CA1266148A - Plasma-resistant polymeric material, preparation thereof, and use thereof - Google Patents
Plasma-resistant polymeric material, preparation thereof, and use thereofInfo
- Publication number
- CA1266148A CA1266148A CA000499386A CA499386A CA1266148A CA 1266148 A CA1266148 A CA 1266148A CA 000499386 A CA000499386 A CA 000499386A CA 499386 A CA499386 A CA 499386A CA 1266148 A CA1266148 A CA 1266148A
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- CA
- Canada
- Prior art keywords
- polymeric material
- organometallic
- layer
- reactive
- reacted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/265—Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
Abstract
PLASMA-RESISTANT POLYMERIC MATERIAL, PREPARATION THEREOF, AND USE THEREOF
ABSTRACT
Plasma-resistant polymeric materials are prepared by reacting a polymeric material containing reactive hydrogen functional groups with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive hydrogen functional groups of the polymeric material, such as hexamethylcyclotrisilazane.
ABSTRACT
Plasma-resistant polymeric materials are prepared by reacting a polymeric material containing reactive hydrogen functional groups with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive hydrogen functional groups of the polymeric material, such as hexamethylcyclotrisilazane.
Description
PLAS~-RESISTA~T POLY~ERIC MATERI~L, PREPAR~TION T~EREOF, A~ID USE TH~REOF
DESCRIPTION
Technical Field The present invention is concerned with polymeric ~aterials which are resistant to oxygen-containing plasma. The present invention is also concerned with a process for obtaining plasma-resistant polymeric materiaLs, as well as their use in lithography. For instance, the materials of 10 the present invention are suitable for use in device fabrication on all optical, e-beam, X-ray, and ion-beam lithography tools and for packaging applications, such as multi-layer ceramic packaging devices.
Background Art In the manufacture of patterned devices, such as semiconductor chips and chip carriers, the processes of etching different layers which constitute the finished product are among the most crucial steps involved. One method widely employed in the etching process is to overlay the surface to be etched with a suitable mask and then to immerse the substrate and mask in a chemical solution which attacks the substrate to be etched while leaving the mask intact. These wet chemical processes suffer from the dificulty of achieving well-defined edges on the etched ~5 surfaces. This is due to the chemicals undercutting thz mask and the formation o~ an isotropic image. In other words, conventional chemical wet processes do not provide the selectivity of direction (anisotropy) considered necessary to achieve optimum dimensional consistent with current processing requirements.
~"soreo~er~ such ~e- -t~nincj ?rocesses are und~sirable ~_cause of the environ~enta1 ~nd saf~ty concerns associat~l therewith.
Accordingly, various so-called "dry proc2sses" have been suggested to improve the process from an environmental vie~point, as well as to reduce the relative cost of the etching. Furthermore, these "dry processes" have the potential advantage of greater process control and higher aspect ratio images.
Such "dry processes" generally involve passing a gas throush a container and creating a plasma in this gas. The species in this gas are then used to etch a substrate placed in the chamber or container. Typical examples of such "dry processes" are plasma etching, sputter etching, and reactive ion etching Reactive ion etching provides well-defined, vertically etched, sidewalls. A particular reactive ion etchirg process is disclosed, for example, in U.S. Patent 4,283,249 to Ephrath, Examples of some dry-developable resists are provided in U.S. Patents 4,426,247 to Tamamura, et al.; 4,433,044 to Meyer, et al.; 4,357,369 to Kilichowski, et al.; 4,430,153 to Gleason, et al.; 4,307,178 to Kaplan, et al.; 4,389,482 to Bargon, et al.; and 4,396,704 to Taylor. In addition, German patent application OS32 15082 (English language counterpart British patent application 2097143) suggests a process for obtaining negative tone plasma resist images~
Such is concerr.ed with a process involving entrapment of a silicon-containing monomer into a host film at the time of exposure to rad ation and requires a processing st~p to ~6~
1 expel the unincorporatecl s:ilicon monomer frorn-the film before plasma developiny of the relief image.
A more recent example of a plasma developable resist is described in U.S. Patent 4,552,833, issued November 12, 1985 (assigned to -the assignee of the present application) in which a method is provided for obtaining a resist which is stated to be radiation sensitive and oxygen plasma developable. Such process involves coating a substrate with a film of a polymer that contains a masked reactive functionality;
imagewise exposing the film to radiation under conditions that cause unmasking of the reactive functionality in the exposed regions of the film;
treating the exposed film with a reactive organometallic reagent; and then developing the relief image by treatment with an oxygen plasma. The specific organometallic reagents described therein are trimethylstannyl chloride, hexamethyldisilazane, and trimethylsilyl chloride. A11 of these materials are monofunctional.
In addition, a method of obtaining a two-layer resist by top imaging a single layer resist is described in Canadian Application No. 495,093, filed November 12, 1985, and assigned to the assignee of the present application) which also employs a monofunctional organometallic reagent.
Summary of Invention According to the present invention, a process is provided which comprises providing a layer of polymeric material wherein the polymeric material contains reactive hydrogen ~unctional groups, or reactive hydrogen functional precursor ~ r. ~>
4 ~
grou?s, or both. ~t least a por~ion of the la~er of poiymeric material is reacted with a multifunctional organometallic material. The organometallic rnaterial cont~ns a~ least two functional groups which are reacted with the above-defined reactive groups of the polymeric material. The reaction is such as to render the reacted portion of the layer reslstant to oxygen plasma. After the reacted portion of the ~ayer is rendered resistant to oxygen plasma, the layer is subjected to a gas plasma atmosphere.
The reacted portion is at least 20 times more resistant to oxygen plasma than the corresponding unreacted polymeric material.
In addition, the present invention is concerned with an improved method for rendering a polymeric material resistant to o~ygen plasma. This process of the present invention includes providing a polymeric material which contains reactive hydrogen functional groups, or reactive hydrogen functional precursor groups, or both. In addition, a liquid composition is provided which contains a multifunctional organometallic material, a solvent for the multifunctional organometallic material, and a solvent for the polymeric material. The multifunctional organometallic material contains at least two functional groups which are reactive with the above-defined reactive groups of the polymeric material. The solvent for the multifunctional organometallic material is nonreactive with the organometallic material. Likewise, the solvent for the polymeric material is nonreactive with the multifunctional organometallic material. The solvent for the polymeric material is provided in an amount which is effective to decrease the reaction time between the multifunctional organometallic material and the polymeric material. The liquid composition and the polymeric material are contacted to there~y render the polymeric material resistant to oxygen 5 ~
plasma.
The present invention is also concerned with a process which co~prises providing a laver of polymeric material on a substrate wherein said polymeric material contains at least reactive hydrogen function groups or reactive hydrogen functional precursor groups reacting at least through 25~ of the depth of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups of said polymeric material.
In addition, the present invention is concerned with cross-linked polymeric materials which are the reaction product of cyclic organometallic compounds having 4, 5 or 6 atoms in the ring such as he~amethylcyclotrisilazar.e and a polymeric material containing reactive hydrogen functional groups, or reactive hydrogen functional precursor groups, or both.
Best and Various Modes for Carrying out Invention The polymeric materials employed in the present invention include a number of different types of materials provided such contain reactive hydrogen functional groups and/or groups which act as precursors to reactive hydrogen functional groups. For instance, the polymeric material can ~5 con~ain moieties which are labile such that upon subjection to certain conditions, such as irradiation, will produce reactive hydrogen functional groups. As used herein, "hydrogen functional groups" includes norm~l hydrogen ~unction groups, as well as its isomer; deuterium functional groups with normal hydrogen being prererred.
r~ 6 E.Yamples of polymers havin~J reacti~e hydrogen functional groups include prepolymerized phenol-formaldehyd- polymers which can be prepared by ~he acid or base catal~zed condensation of formaldehyde with an excess of a phenol having the formula:
OH
A~9 wherein A and B, individually, are hydrogen or al~yl g~oup containing 1-6 carbon atoms. Such phenolic-formaldehy~e polymers are referred to as novolak poly~ers. In additicn, such phenol-novolak compositions can contain a diazo ~etone sensitizer as known in the art. Such sensitizers and polymers are described, for example, in U.S. Patents 3,046,118; 3,046,121; 3,106,465i 3,201,239; and 3,666,473 .
The sensiti ers are diazo ketones having diazo and keto group at adjacent positions on the molecules, such as the naphthoquinone-(1,2)-diazide sulfonic acid esters which are reported in U.S. Patent 3,201,239 which has the formula:
~=~v-cR3 RlSO2-O ~ OH
in which Rl is a naphthoquinone~(1,2)-diazide radical, R2 is selected from the group of hydrogen and hydroxv', and R3 is from the group of hydrogen, alkyl, aryl, alkoxy, arylo~y, amino, and heterocyclic groups.
Examples of sensitizers are also reported in U.S. Patent 3,046,11~ ~hich has the for~ula:
,Y X
Xl = ~ ~52-0-Y-O-SO2~
wherein X and Xl are ~l2 or O, those attached to ~he same ring being different, and Y is an organic linkage containing at least one arylene, substituted arylene, or heterocyclic radical; U.S. Patent 3,046,121 which has the formula Il X
r ~ 1 wherein X and Xl are from the group of N2 and O and are different. Y is hydrogen or halogen and R is a substituted or unsubstituted aryl or heterocyclic radical; and U.S.
Patent 3,106,465 which has one of the formula:
R
D -SO - u ~ rC~ C / D SO ~ /~
X OH ~ C\
R
1~ wherein D stands for naphthoquinone-(1,2)-diazide radical; X
stands for H or OH; R stands for a member of the group of hydrogen, ORl, NR2R3, alkyl-, aryl-, and heterocyclic radicals; Rl is an alkyl or aryl; R2 and R3 are a hydrogen alkyl or aryl, R2 equallng R3 or being different from R3.
E.~amples of such com~ounds are 2,3,4-trihydroxybenzophenone esters of l-oxo-2~naphthalene-5 sulronic acid. The sensitizers, when used, are generallv employed in amounts or YQ~4-10~
abou~ 125 to about 30~ by wei-~ht of the pol,~meric com?onen~_ of tne composltion.
Examples of reactive hydrogen functlonal groups include O~, COOH, N~, and SH groups. Also, epoxide groups which are S capable of undergoing ring opening and forming OH groups are suitable reactive hydrogen functional precursor groups.
Examples of other polymers include polyvinylpyrrolidone, polyvinylalcohol, polymers of p-hydroxystyrene, melamino polymers, homopolymers and copolymers of moncethylenically unsaturated acids, copolymers of alkyl methacrylates containing about 1-4 carbon atoms in the alkyl group, and a monoethylenically unsaturated acid. The monoethylenically unsaturated acid can be acrylic acid, methacrylic acid, or crotonic acid. Usually the polymer contains from about 50 to about 99.5 mole percent of the alkyl methacrylate and about 50 to about 0.5 mole percent of the unsaturated acid.
These mole percents are based upon the total moles of the alkyl methacrylate and acid in the pol~mer. Examples of such polymers can be found in U.S. Patent 3,98~,582, ~0 ~
Polymers containinq labile groups which are capable upon excitation, such as upon irradiation of generating reactive hydrogen groups include O-nitrobenzene derivatives and polymers capable of photo-fries rearrangement. Upon irradiation, acids, alcohols, and/or amines with reactive hydrogens are generated. Examples of such materials are:
Y0984-l0l 9 ~
H I~H
~; h~ C
R2 o ~C' O h`/ _c=~ ~NO
N02 Rl -0-C-N-R3 R2 ~ ,C,H
~ --, R3- N- H+C02 ~ NO
Rl Rl hv ~ R
wherein R1, R2, R3, and R5 = H, alkyl, aryl, or part of a polymer backbone and R4 = H, CnH2nll wherein n ranges from 1 to about 5 phenyl or substituted phenyls.
~6~
O O
f n~ 2 hv ~ C-OH
~ MOISTURE ~ ~f !
Rl . R2 Rl R2 H~ H
-lCl-R5~ ~ R4 ~ ~3 R~J ~ ~-R5 C
- O
Il ~-R~ 5~ QH 01 Rl Rl O-S-R~ Rl 11.
wherein R1, R2, R3, and R5 = H, alkyl, aryl, or part of a polymer backbone and R4 - H, CnH2n~1 from 1 to about 5, phenyl or substituted pheny:Ls.
Materials of the above type can be used alone or in combination with compatible polymeric materials.
Compounds such as substituted 0-nitrobenzaldehyde, esterified phenols, and diazoquinone derivatives can be mixed together with polymers which have no labile or reactive hydrogens. For example, polymethylmethacrylate, styrene-butadiene rubbers, polymethylisopropenyl ketone (PMIPK), and polystyrene and its derivatives. Upon irradiation, the molecules which are sensitive to the irradiation undergo rearrangement to yield products with labile and reactive hydrogens. The labile and reactive hydrogens are then subsequently reacted with an organometallic reagent pursuant to the process of the present invention.
Examples of such particular polymers include acetylated polyvinylphenol, poly (p-formyl~ oxystyrene, copolymers prepared from p-formyl oxystyrene, poly (t-butyl) methacrylate, poly (t-butyloxycarbonyloxystyrene), and copolymers from t-butylmethacrylate or t-butyloxycarbonyl-oxystyrene. Disclosures of such polymers can be found in Canadian Patent Application 495,093, filed November 12, 1985; U.S. Patent No.
4,552,833, issued November 12, 1985; and Canadian Application No. 494,157, filed October 29, 1985 by Hefferon et al, and entitled "Method of Creating Patterned Multilayer Films For Use In Production Of Semiconductor Circuits And Systems"; and all assigned to the assignee of the present application.
The multifunctional organometallic material employed pursuant to the present invention must contain or be capable of supplying at least two functional groups which are reactive wlth the reactlve groups of ~he polymeric material.
Examples of suitable metallic portlons of the organome~alli~
material are Group III A metals, Group IV A metals, Group IV
B metals, ana Group VI B metals. Examples of Group IV ~
s metals are tin, germanium, and silicon. Examples of Group IV s metals are titanium and zirconium. Examples of Group VI B metals are tungs-ten and molybdenum. An example of a Group III A metal is aluminum. The preferred metallic portions are titanium, silieon, and tin, with the most preferred being silicon.
The reaetive groups o~ the organometallic compound include sueh reaetive groups as hydroxy, amino, mercapto, and halogen; and groups eapable of supplying reactive groups inelude alkoxy groups, such as methoxy and ethoxy which hydrolyze to form OH groups.
E~amples of suitable organometallie eompounds inelude the following:
/ N
\si/ si RI/ l ~RI
RII N 1.
Si~ ~ n RI RII
wherein eaeh R and RI, individually, is H, alkyl, eyeloalkyl, aryl, halo-substituted alkyl, halo, or halo-substitu~ed aryl; each RI~, individually, is ~1, alkyl, or aryl, and n is a whole number integer~ 1 and prererably 1 or 2.
R~l \ S i \S i R ~ r o o
DESCRIPTION
Technical Field The present invention is concerned with polymeric ~aterials which are resistant to oxygen-containing plasma. The present invention is also concerned with a process for obtaining plasma-resistant polymeric materiaLs, as well as their use in lithography. For instance, the materials of 10 the present invention are suitable for use in device fabrication on all optical, e-beam, X-ray, and ion-beam lithography tools and for packaging applications, such as multi-layer ceramic packaging devices.
Background Art In the manufacture of patterned devices, such as semiconductor chips and chip carriers, the processes of etching different layers which constitute the finished product are among the most crucial steps involved. One method widely employed in the etching process is to overlay the surface to be etched with a suitable mask and then to immerse the substrate and mask in a chemical solution which attacks the substrate to be etched while leaving the mask intact. These wet chemical processes suffer from the dificulty of achieving well-defined edges on the etched ~5 surfaces. This is due to the chemicals undercutting thz mask and the formation o~ an isotropic image. In other words, conventional chemical wet processes do not provide the selectivity of direction (anisotropy) considered necessary to achieve optimum dimensional consistent with current processing requirements.
~"soreo~er~ such ~e- -t~nincj ?rocesses are und~sirable ~_cause of the environ~enta1 ~nd saf~ty concerns associat~l therewith.
Accordingly, various so-called "dry proc2sses" have been suggested to improve the process from an environmental vie~point, as well as to reduce the relative cost of the etching. Furthermore, these "dry processes" have the potential advantage of greater process control and higher aspect ratio images.
Such "dry processes" generally involve passing a gas throush a container and creating a plasma in this gas. The species in this gas are then used to etch a substrate placed in the chamber or container. Typical examples of such "dry processes" are plasma etching, sputter etching, and reactive ion etching Reactive ion etching provides well-defined, vertically etched, sidewalls. A particular reactive ion etchirg process is disclosed, for example, in U.S. Patent 4,283,249 to Ephrath, Examples of some dry-developable resists are provided in U.S. Patents 4,426,247 to Tamamura, et al.; 4,433,044 to Meyer, et al.; 4,357,369 to Kilichowski, et al.; 4,430,153 to Gleason, et al.; 4,307,178 to Kaplan, et al.; 4,389,482 to Bargon, et al.; and 4,396,704 to Taylor. In addition, German patent application OS32 15082 (English language counterpart British patent application 2097143) suggests a process for obtaining negative tone plasma resist images~
Such is concerr.ed with a process involving entrapment of a silicon-containing monomer into a host film at the time of exposure to rad ation and requires a processing st~p to ~6~
1 expel the unincorporatecl s:ilicon monomer frorn-the film before plasma developiny of the relief image.
A more recent example of a plasma developable resist is described in U.S. Patent 4,552,833, issued November 12, 1985 (assigned to -the assignee of the present application) in which a method is provided for obtaining a resist which is stated to be radiation sensitive and oxygen plasma developable. Such process involves coating a substrate with a film of a polymer that contains a masked reactive functionality;
imagewise exposing the film to radiation under conditions that cause unmasking of the reactive functionality in the exposed regions of the film;
treating the exposed film with a reactive organometallic reagent; and then developing the relief image by treatment with an oxygen plasma. The specific organometallic reagents described therein are trimethylstannyl chloride, hexamethyldisilazane, and trimethylsilyl chloride. A11 of these materials are monofunctional.
In addition, a method of obtaining a two-layer resist by top imaging a single layer resist is described in Canadian Application No. 495,093, filed November 12, 1985, and assigned to the assignee of the present application) which also employs a monofunctional organometallic reagent.
Summary of Invention According to the present invention, a process is provided which comprises providing a layer of polymeric material wherein the polymeric material contains reactive hydrogen ~unctional groups, or reactive hydrogen functional precursor ~ r. ~>
4 ~
grou?s, or both. ~t least a por~ion of the la~er of poiymeric material is reacted with a multifunctional organometallic material. The organometallic rnaterial cont~ns a~ least two functional groups which are reacted with the above-defined reactive groups of the polymeric material. The reaction is such as to render the reacted portion of the layer reslstant to oxygen plasma. After the reacted portion of the ~ayer is rendered resistant to oxygen plasma, the layer is subjected to a gas plasma atmosphere.
The reacted portion is at least 20 times more resistant to oxygen plasma than the corresponding unreacted polymeric material.
In addition, the present invention is concerned with an improved method for rendering a polymeric material resistant to o~ygen plasma. This process of the present invention includes providing a polymeric material which contains reactive hydrogen functional groups, or reactive hydrogen functional precursor groups, or both. In addition, a liquid composition is provided which contains a multifunctional organometallic material, a solvent for the multifunctional organometallic material, and a solvent for the polymeric material. The multifunctional organometallic material contains at least two functional groups which are reactive with the above-defined reactive groups of the polymeric material. The solvent for the multifunctional organometallic material is nonreactive with the organometallic material. Likewise, the solvent for the polymeric material is nonreactive with the multifunctional organometallic material. The solvent for the polymeric material is provided in an amount which is effective to decrease the reaction time between the multifunctional organometallic material and the polymeric material. The liquid composition and the polymeric material are contacted to there~y render the polymeric material resistant to oxygen 5 ~
plasma.
The present invention is also concerned with a process which co~prises providing a laver of polymeric material on a substrate wherein said polymeric material contains at least reactive hydrogen function groups or reactive hydrogen functional precursor groups reacting at least through 25~ of the depth of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups of said polymeric material.
In addition, the present invention is concerned with cross-linked polymeric materials which are the reaction product of cyclic organometallic compounds having 4, 5 or 6 atoms in the ring such as he~amethylcyclotrisilazar.e and a polymeric material containing reactive hydrogen functional groups, or reactive hydrogen functional precursor groups, or both.
Best and Various Modes for Carrying out Invention The polymeric materials employed in the present invention include a number of different types of materials provided such contain reactive hydrogen functional groups and/or groups which act as precursors to reactive hydrogen functional groups. For instance, the polymeric material can ~5 con~ain moieties which are labile such that upon subjection to certain conditions, such as irradiation, will produce reactive hydrogen functional groups. As used herein, "hydrogen functional groups" includes norm~l hydrogen ~unction groups, as well as its isomer; deuterium functional groups with normal hydrogen being prererred.
r~ 6 E.Yamples of polymers havin~J reacti~e hydrogen functional groups include prepolymerized phenol-formaldehyd- polymers which can be prepared by ~he acid or base catal~zed condensation of formaldehyde with an excess of a phenol having the formula:
OH
A~9 wherein A and B, individually, are hydrogen or al~yl g~oup containing 1-6 carbon atoms. Such phenolic-formaldehy~e polymers are referred to as novolak poly~ers. In additicn, such phenol-novolak compositions can contain a diazo ~etone sensitizer as known in the art. Such sensitizers and polymers are described, for example, in U.S. Patents 3,046,118; 3,046,121; 3,106,465i 3,201,239; and 3,666,473 .
The sensiti ers are diazo ketones having diazo and keto group at adjacent positions on the molecules, such as the naphthoquinone-(1,2)-diazide sulfonic acid esters which are reported in U.S. Patent 3,201,239 which has the formula:
~=~v-cR3 RlSO2-O ~ OH
in which Rl is a naphthoquinone~(1,2)-diazide radical, R2 is selected from the group of hydrogen and hydroxv', and R3 is from the group of hydrogen, alkyl, aryl, alkoxy, arylo~y, amino, and heterocyclic groups.
Examples of sensitizers are also reported in U.S. Patent 3,046,11~ ~hich has the for~ula:
,Y X
Xl = ~ ~52-0-Y-O-SO2~
wherein X and Xl are ~l2 or O, those attached to ~he same ring being different, and Y is an organic linkage containing at least one arylene, substituted arylene, or heterocyclic radical; U.S. Patent 3,046,121 which has the formula Il X
r ~ 1 wherein X and Xl are from the group of N2 and O and are different. Y is hydrogen or halogen and R is a substituted or unsubstituted aryl or heterocyclic radical; and U.S.
Patent 3,106,465 which has one of the formula:
R
D -SO - u ~ rC~ C / D SO ~ /~
X OH ~ C\
R
1~ wherein D stands for naphthoquinone-(1,2)-diazide radical; X
stands for H or OH; R stands for a member of the group of hydrogen, ORl, NR2R3, alkyl-, aryl-, and heterocyclic radicals; Rl is an alkyl or aryl; R2 and R3 are a hydrogen alkyl or aryl, R2 equallng R3 or being different from R3.
E.~amples of such com~ounds are 2,3,4-trihydroxybenzophenone esters of l-oxo-2~naphthalene-5 sulronic acid. The sensitizers, when used, are generallv employed in amounts or YQ~4-10~
abou~ 125 to about 30~ by wei-~ht of the pol,~meric com?onen~_ of tne composltion.
Examples of reactive hydrogen functlonal groups include O~, COOH, N~, and SH groups. Also, epoxide groups which are S capable of undergoing ring opening and forming OH groups are suitable reactive hydrogen functional precursor groups.
Examples of other polymers include polyvinylpyrrolidone, polyvinylalcohol, polymers of p-hydroxystyrene, melamino polymers, homopolymers and copolymers of moncethylenically unsaturated acids, copolymers of alkyl methacrylates containing about 1-4 carbon atoms in the alkyl group, and a monoethylenically unsaturated acid. The monoethylenically unsaturated acid can be acrylic acid, methacrylic acid, or crotonic acid. Usually the polymer contains from about 50 to about 99.5 mole percent of the alkyl methacrylate and about 50 to about 0.5 mole percent of the unsaturated acid.
These mole percents are based upon the total moles of the alkyl methacrylate and acid in the pol~mer. Examples of such polymers can be found in U.S. Patent 3,98~,582, ~0 ~
Polymers containinq labile groups which are capable upon excitation, such as upon irradiation of generating reactive hydrogen groups include O-nitrobenzene derivatives and polymers capable of photo-fries rearrangement. Upon irradiation, acids, alcohols, and/or amines with reactive hydrogens are generated. Examples of such materials are:
Y0984-l0l 9 ~
H I~H
~; h~ C
R2 o ~C' O h`/ _c=~ ~NO
N02 Rl -0-C-N-R3 R2 ~ ,C,H
~ --, R3- N- H+C02 ~ NO
Rl Rl hv ~ R
wherein R1, R2, R3, and R5 = H, alkyl, aryl, or part of a polymer backbone and R4 = H, CnH2nll wherein n ranges from 1 to about 5 phenyl or substituted phenyls.
~6~
O O
f n~ 2 hv ~ C-OH
~ MOISTURE ~ ~f !
Rl . R2 Rl R2 H~ H
-lCl-R5~ ~ R4 ~ ~3 R~J ~ ~-R5 C
- O
Il ~-R~ 5~ QH 01 Rl Rl O-S-R~ Rl 11.
wherein R1, R2, R3, and R5 = H, alkyl, aryl, or part of a polymer backbone and R4 - H, CnH2n~1 from 1 to about 5, phenyl or substituted pheny:Ls.
Materials of the above type can be used alone or in combination with compatible polymeric materials.
Compounds such as substituted 0-nitrobenzaldehyde, esterified phenols, and diazoquinone derivatives can be mixed together with polymers which have no labile or reactive hydrogens. For example, polymethylmethacrylate, styrene-butadiene rubbers, polymethylisopropenyl ketone (PMIPK), and polystyrene and its derivatives. Upon irradiation, the molecules which are sensitive to the irradiation undergo rearrangement to yield products with labile and reactive hydrogens. The labile and reactive hydrogens are then subsequently reacted with an organometallic reagent pursuant to the process of the present invention.
Examples of such particular polymers include acetylated polyvinylphenol, poly (p-formyl~ oxystyrene, copolymers prepared from p-formyl oxystyrene, poly (t-butyl) methacrylate, poly (t-butyloxycarbonyloxystyrene), and copolymers from t-butylmethacrylate or t-butyloxycarbonyl-oxystyrene. Disclosures of such polymers can be found in Canadian Patent Application 495,093, filed November 12, 1985; U.S. Patent No.
4,552,833, issued November 12, 1985; and Canadian Application No. 494,157, filed October 29, 1985 by Hefferon et al, and entitled "Method of Creating Patterned Multilayer Films For Use In Production Of Semiconductor Circuits And Systems"; and all assigned to the assignee of the present application.
The multifunctional organometallic material employed pursuant to the present invention must contain or be capable of supplying at least two functional groups which are reactive wlth the reactlve groups of ~he polymeric material.
Examples of suitable metallic portlons of the organome~alli~
material are Group III A metals, Group IV A metals, Group IV
B metals, ana Group VI B metals. Examples of Group IV ~
s metals are tin, germanium, and silicon. Examples of Group IV s metals are titanium and zirconium. Examples of Group VI B metals are tungs-ten and molybdenum. An example of a Group III A metal is aluminum. The preferred metallic portions are titanium, silieon, and tin, with the most preferred being silicon.
The reaetive groups o~ the organometallic compound include sueh reaetive groups as hydroxy, amino, mercapto, and halogen; and groups eapable of supplying reactive groups inelude alkoxy groups, such as methoxy and ethoxy which hydrolyze to form OH groups.
E~amples of suitable organometallie eompounds inelude the following:
/ N
\si/ si RI/ l ~RI
RII N 1.
Si~ ~ n RI RII
wherein eaeh R and RI, individually, is H, alkyl, eyeloalkyl, aryl, halo-substituted alkyl, halo, or halo-substitu~ed aryl; each RI~, individually, is ~1, alkyl, or aryl, and n is a whole number integer~ 1 and prererably 1 or 2.
R~l \ S i \S i R ~ r o o
2.
si si I ~ \ / \ ~I
wherein each R and RI, individually, is H, alkyl, S cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually is H, alkyl or aryl; and X is 0, Si, or N-R"~
R \ ¦ / R
Si N - Si rI / ~
\ Si ~ N ~
RI / \ m ' R RI
14 3 ~ 4B
wherein each R ana RI, individuall,~, is ~, alkyl, cycloal~yl, aryl, halo, halo-suhstituted alkyl, or halo-substituted aryl; each ~II, individually, is H, al~yl, or aryl; and m is a whole nul~er integer >1 and prererahly 1 or 2.
~ \ I N I RII RRII
RII ~ ~ ~\ RrI 4.
N-R N-R N R
~I I I 1I I ,~ R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and each RII, individually, is H, alkyl, or aryl.
RII R R RII R
R
T~5i- N - Si t-O - S )p O - Si - N - Si \
R - ~ N-R R - N N R 5 R ~ R R \ I I ",R
~1 ~ Si I Sl I I~ N - Si wherein each R and RI, individually, is H, alkyl, Y09~4-1~1 cycloalkyl, aryl, halo, halo-substituted alkyl, cr halo-substituted aryl; each RII, individually, is ~, alXyl, or aryl; and p is a whole number in~eger of >1 and preferably 1-~o R R RII R RII RI
/ N ~ i N ( S N )r Si ~ 6 wherein each R and RI, individually, is H, aLkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually, is H, alkyl, or aryl; and r is a whole number integer of 0-102, preferably 1-4.
R R
R li ( CH2 )5 - --7 Si - RI
H- 1~ N '. 7-l R
R - ~i ( CH~ ;i /
R L
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and each s, individually, is a whole nu~ber integer >l, and preferably 1 or 2.
Y~984-lOl R Sl ¦ ~ Si ~ 8-H --N M - ~
\ I i XI - si wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo-substituted aryl, or halo; and XI is (-CH2-)t, or ~ y ~
wherein t is a whole number integer of >1 and preferably 1-4; and Y is 0, NH, or S.
wherein each R and R , individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and v is a wnole number integer of >1 and preferably 1-4.
17 ~ 8 ~c C 1 o .
~h - T 7I I I Ph N ~ N R N ---= --=~J
wherein each R anc RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl.
O R RIII
RTII C - N - Si ' - C RTII 11 wherein~each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-su~stituted alkyl, or halo-substituted aryl, and each RIII, individually, is alkyl.
\ Si/- R
H j l l R ~ / H 12.
~ : / N - Si ~ - N - S ~ RII
~wherein each R and RI, individually, is H, alkyl, ~ ,~
: ; :
Y0984-10l ~, : ~ :
::
:~:
cycloalkyl, ar~yl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually, is H, al'~yl, or aryl; and w is a whole nu~ber integer >1 and preferably 1-4.
~ H
/c2~
H C f i -_ N - Si CH
2 7-H NH 13.
2~ Ti fH
H C -CH H2C - CH ~
wherein z is a whole number integer of 0-4 and prererably 0-2.
r~S~ \
R O
wherein R is H, alkyl, cycloalkyl, aryl, halo, halo-substltuted alkyl, or halo-substituted aryl.
Y0984-lOI
1 9 ~.~6~
R \ / ~
R \ N3 15.
wherein each R and RI, individualLy, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl.
H ~I H C H R H
L
wherein each R and RI is H, alkyl, aryl, cycloalkyl, halo, halo-substituted alkyl, or halo-substituted aryl; and a is a whole number integer >1 and preferably 1-4.
~ N ~i N ~ 17.
RI
wherein R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substitu~ed alkyl, or halo-substituted aryL.
yI i _ ~I 18 wherein each yI~ individually, is _ N \ N _ j ~=N/ or --U ¦ , ara RI and R, individually, is H, alkyl, aryl, cycloalkyl, halo, halo-substituted alkyl, or halo substituted aryl.
19.
N - Si ~ N
wherein R and R , individually, i~ H, al~yl, cycloalkyl, S aryl, halo, halo-substituted alkyl, or halo-substituted ary1.
:~
RIV R RIV
~VI - C ~ i . N -- C - - RJI 20.
OSi(R )3 RI OSi(R )3 wherein R and RI, individually, is H, alkyl, aryl, cycloalkyl, halo, halo.~substituted akyl, or halo-substituted aryl; each RI , individually, is H or alkyl; each R , individually, is H or alkyl; and eah RVI, individually, is alkyl or CX3(X=F, Cl, Br, I).
R - f _~7 - Si - N - C RVI 21.
GSi(R )3 R ISi(R )3 wherein R and RI, individually, is H, alkyl, aryl, cycloalkyl, halo, halo-substituted akyl, or halo-substituted aryl; each RIV, each RV, individually, is H or alkyl; and each R , individually, is alkyl or CX3(X=F,Cl, Br, I).
O R O
RVII -CHN Si NHI - ---RVII 22.
1~
R
22 ~
wherein R and RI, individually, is H, alkyl, aryL, cycloalkyl, halo, halo-substituted akyl, or halo-substitutec~
aryl; and each R II, individually, is alkyl.
pIX
(~VIII)2N~ Si _N(pVIII) 23.
~I
wherein each RIX, individually, is alkyl; ana eacn RVIII~
S individually, is alkyl.
N RII 2~.
R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo or halo-substituted aryl; each RII, individually, is H, alkyl or aryl.
. RII ~ / \ N RII and 25.
H2C (CH2)a .
~ ~ Yo984-101 :::
dimers and polymers thereo~ wherein each R and RI, indi~Jidually, ls H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo, or halo-subs~ituted aryl, each R I, individually, is H, alkyl or aryl; and a is 1, 2, or 3.
~ (R \
R ~I~ RI ~6-wherein b is a whole number integer of 1-5; each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyL, halo, or halo-substituted aryl; each X, individually, is halo, SH, OH, ORX, and NH and Rx is alkyl, 1-5 carbon atoms, and preferably ethyl or methyl.
R \ RI
(R)3 - Si - N < / Si (R)3 27.
/Sl R R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl r halo, or halo-substituted aryl.
Examples of suitable alkyl groups in the above formulas are ~ alkyl groups containing 1-12 carbon atoms and preferably 1-4 carbon atoms. Specific examples of such are methyl, ethyl, propyl, butyl, and octyl. The most preferred alky groups are methyl and ethyl.
Y098b- 101 ' ~;~mples of suit~ble c~clo~l~yl groups are cyclohe~l an~
cycloheptyl.
E~amples of suitable aryl groups are phenyl, tol~l, xylyl, and napthyl radicals.
Examples of suitable halo radicals are F, Cl, Br, and I.
E~amples of suitable halo-substituted alkyl groups are l,l,l-trifluoropropyl, and chloromethyl.
Examples of suitable halo-substituted aryl groups are chlorophenyl and dibromophenyl.
In many applications of the use of the products of the present invention, it is preferred that the orsanometallic compound not include any halogen component such as chlorine to assure against the possibiLity of causing corrosion due to the potential formation of some corrosive halide gas.
The preferred organometallic compounds are the cyclic organo silicon compounds and more preferably hexamethylcyclotri-silazane.
The amount of the organometallic material employed must be sufficient to provide the desired degree of cross-linking and plasma resistance. Usually, the relative amount of the organometallic material to the polymeric material provides at least about 1 part by weight of the metallic component (e.g. - Si) per 20 parts of the polymeric material, and up to about 1 part by weight of the metallic component per 2 25 parts by weight of the polymeric material, and preferably about 1 part by weight of the metallic component per 15 parts of the pol~meric material to about 1 part by weight of the metaliic component per 4 parts by weight of the Y09~4-lOl l polymeric material.
The cross--linked polymeric materials prepare~ in accordance with the present invention are resistant to oxygen plasma and are extremely stable when exposed to elevated temperatures. The cross-linked polymeric materials of the present invention are at least about 20 times, preferably at least about 50 times, and in many cases, at least about 100 times as resistant to oxygen plasma as is the corresponding noncross-linked polymeric material. Cross-linked polymeric materials, such as novolak resins in accordance with the present invention have thermal stabilities of up to about 400C; whereas, polymeric materials prepared with monofunctional organometallic materials, such as discussed in aforementioned ~.S. Patent 4,552,883, do not have thermal stabilities above about 200C.
Moreover, even upon decomposition, the cross-linked materials of the present invention, and particularly the novolak resins, do not form volatile materials at temperatures up to about 400C as occur when monofunctional organometallic compounds are employed in the reaction. The materials of the present invention exhibit good solvent resistance. Accordingly, materials of the present invention are useful in environments other than those which involve exposure to an oxygen-containing plasma. For instance, materials of the present invention can be used in applications which require materials to be resistant to high temperature.
The materials of the present invention can be prepared by reacting the polymeric material with the multifunctional organometallic material in either the vapor phase or preferably dissolved in a suitable solvent. In the preferred aspects of the present invention, the polymeric material is already in the form of a film or layer when contacted with the multifunctional organometallic material.
YO9-84~101 For instance, th~ pol~meric r~aterial, particularl~ ,/hen it is to be employed in a lithoyraphic process, is applied to a desired substrate to provide films generally about 1500 angstroms to about l mil thick, such as by spraying, spinning, dipping, or any o-ther known means of application of coating. Some suitable substrates include those Ised in the fabrication of semiconduc~or devices or integrat2d circuits whlch include wafers or chips overcoated with oxides and nitrides (silicon oxide and/or silicon nitride for diffusion masks and passivation) and/or metals normally employed in the metallization steps ror forming contacts anc conductor patterns on the semiconductor chip.
~loreover, the polymeric materials can be used as coatings on those substrates employed as chip encapsulants and including ceramic substrates and, especially, multilayer ceramic devices. Also included are dielectric substrates which can be thermoplastic and/or thermosetting polymers.
Typical thermosetting polymeric materials includ2 epoxv, phenolic-base materials, polyamides, and polyimides. The dielectric materials can be molded articles of the polymers containing fillers and/or reinforcing agents, such as glass-filled epoxy or phenolic-base materials. Examples of some phenolic-type materials include copolymers or phenol r resorcinol, and cresol. Examples of some suitable thermoplastic polymeric materials include polyolefins, such as polypropylene, polysulfones, polycarbonates, nitrile rubbers, and ABS polymers.
The reaction bet~een the organometallic material is usually carried out in about 5 minutes to about l hour depending upon the relative reactivities of the materials employea, the solvent system employed, and the depth through the film to which it is desired to cause the cross-linking. ~or instance, it may be desired to onl~ effect the reaction through a portion of the la~er of the pol~meric materi~l.
In most applications, at least about 25~, and preferably at least 50% of the total thickness of the film is cross-linked. In many instances, the entire thickness, or at least substantially -the entire film thickness, is cross-linked. ~sually the thickness reacted is at least 0.3 microns. Generally thicknesses above about 25 microns are not necessary for the applications to which the films are most useful. Preferably thickness is about 0.4 to about 10 microns. Most preferably the thickness is about 0.5 to about 5 microns.
In the preferred aspects of the present invention, the organometallic material is dissolved in an organic solvent which is non-reactive with the organometallic material. It is preferred that the inert organic solvent be aprotic. ~he most preferred solvents are the aromatic hydrocarbons and substituted aromatic hydrocarbons including benzene, toluene, xylene, and chlorobenzene. Other solvents include N-methyl pyrrolidone; y-butyrolactone; acetates , such as butyl acetate and 2-methoxy acetate; ethers; and tetrahydrofuran. In addition, the solvent is preferably selected so that it has some ability to diffuse enough through the polymeric material to provide the needed contact between the organometallic material and polymeric material.
It is preferred that this solvent be only a partial rather than a good solvent for the polymeric material. Accordingly, the choice of the polymeric material will have some effect upon the choice of the solvent used for best results.
In the preferred aspects of the present invention, the solvent component also includes a solvent in which the polymerlc material is readily soluble in when the major portion of the solvent component is a non solvent or only a Y09~4-101 2 ~
par~ial so1~ent ~or the pol~merlc rnaterial. The solvent for the ~ol~meric material is employed in arnoun~s effec~ive to decrease the necessary reaction time between the multifunctional organometallic material and the polymeric material. The solvent for the polymeric material must be non-reactive with the multifunctional oryanometallic material. Examples of suitable solvents for the pol~meric material to be employed are N-meth~l pyrrolidone y-butyrolactone and acetates such as cellosolve acetate, butyl acetate, a~d 2-methoxy ethyl acetate.
The solvent for the polymeric material is employed in relatively minor amounts so as not to remove or dissolve the polymeric film. Preferred amounts of the organic solvent for the polymeric material are about .01% to about 25~ by volume, and more preferably about 0.25~ to about 5~, based on the total amount of organic solvent in the liquid composition. The total amount of solvent in the liquid composition is usuall~ about 75% to about 98~ and preferably about 95~ to about 96% based upon the total of the solvent and organometallic material in the liquid composition. Use of elevated temperatures also enhances the diffusion through the polymeric material.
An example of a process employing the materials of the present invention involves coating a thin layer of about 0.
to about 10 microns of a photoresist material over a polymeric surface as the substrate. Examples of suitable photoresist materials include the above-described phenolic-formaldehyde photoresist containing quinone sensitizers.
Such materiais are preferably subjected to elevated temperatures of about 80C ror about 15 minutes to effect a precuring or prebake of the composition.
Y0984~
2 g The reslst is then e~posed to ultraviGlet Light and ~eveloped ln an ~lkaline soLution to remove those por~ions of the resist whlch were exposed to the ultraviolet light.
Next, the developed patterned images are contacted with the organometallic materials, such as by flooding the substrate on a spinner in a solution of the organometallic material solu-tion for about 1 minu~e to about 60 minutes.
The composite is then washed in a solvent, such as xylene, and baked at about 125C for about 1 hour.
Next, the composite is placed in a reaction chamber which is then evacuated and filled with oxygen. The pressure in the reaction chamber is about 10 millitorr and the gas is introduced into the reaction chamber at a flow rate of about 0.02 standard liters per minute. A plasma is formed in the oxygen gas by coupling radio frequency power of about 0.02 kilowatts to the plasma and is continued for about 10-250 minutes. The oxygen-containing plasma can be from oxygen, oxygen-inert gas mixtures (e.g. - argon), oxygen-halocarbon mixtures (e.g. - CF4), and oxygen-hydrocarbon, as is well-known.
~he portion of the organic polymeric substrate which is protected by the reaction product resists the o~ygen plasma and remains intact. That portion of the organic polymeric substrate not protected by the reaction proauct is etched by the oxyqen plasma.
The following non-limiting e~amples are presented to further illustrate the present invention.
E~ lPLE 1 A layer of about 1 micron thlck of Shipley ~Z-1350 positive photoresist, which is an m-cr2sol formaldehyde novolak polymer containing about 15~ by weight of 2-diazo-1-naphthoquinone-5-sulphonic acid ester, is coat~d onto a substrate ot a polyimide of about 2 microns thick.
The photoresist is prebaked at about 80C for about 15 minutes.
The resist is then imagewise exposed to ultrzviolet light and developed in an alkaline solution to remove those portions of the resist which were exposed to the ultraviolet light.
Next, the developed patterned image is reacted with hexamethylcyclotrisilazane by flooding the substrate on a spinner in a solution o~ 30% hexamethylcyclotrisilazane in chlorobenzene for about 10 minutes at room temperature.
The composite is then washed in xylene and baked at about 80C for about l hour.
Next, the composite is placed in a reaction chamber which is then evacuated and filied with oxygen. The pressure in the reaction chamber is about lO millitorr and the gas is introduced into the reaction chamber at a flow rate of about 0.02 standard liters per minute. The oxygen is disassociated by coupling radio frequency power of about 25 0.02 kilo~atts to the plasma and is continued for about 15 minutes.
The portion of the substrate which is protected by the reaction product resists the oxygen plasma and remains *Tr~ade Mark i$~4~
r 31 intact. That portion of the substrate not protectea ~y th reaction product is etched bv the oxygen plasma.
E,YAi~PLE 2 Example 1 is repeated, except that the organome~allic composition is a 10~ solution of hexamethylcyclotrisilazane in xylene. The reaction of the hexamethylcyclotrisilazane with the polymeric material is carried out at about 40C for about 30 minutes.
EX~MPLE 3 Example 2 is repeated, except that the organometallic composition is a 10% solution of hexamethylcyclotrisilazane in xylene containing 1~ by weight of N-methylpyrrolidone.
The reaction time is reduced to only 10 minutes.
E~AMPLE 4 Example 2 is repeated, except that the organometallic composition is a 10~ solution of hexamethylcyclotrisilazane in xylene containing 1% of y-butyrolactone. The reaction time between the silazane and polymeric material is reduced to 10 minutes.
A comparison of Examples 3 and 4 with Example 2 illustrates the improved results obtained by incorporating small amounts of a solvent for the polymeric material.
E'~AMPLE 5 Example 2 is repeated, except that the polymeric material is Kodak~820 positive resist. The reaction is carried out at about 75~C in about 45 minutes.
*Trade Mark ~Y0984-lOI
1~6~
EX~ PLE 6 .
Example 2 is repeated, except that the organometaLlic composition is a 10o solution of hexamethylcyclotrisilazane in xylene containing 5% by weight o~ rl-methylpyrrolidone and the polymeric material is Kodak 820 positive resist. The reaction is carried out at about 40C in about 10 minutes.
Example 2 is repeated, except that the organometallic composition is a 10% solution of hexamethlycyclotrisilazane in y-butyrolactone and the polymeric material is a terpolymer of methylmethacr~late, methacrylic acid, and methacrylic anhydride. The reaction is carried out at about 40C in about 10 minutes.
EXA~IPLE 8 Example 2 is repeated, except that the organometallic composition is a 10% solution of octamethylcyclotetrasili-zane in xylene. The reaction is carried out at about 40C
for about 10 minutes.
Example 2 is repeated, except that the organometallic composition is a 10% solution of 1,3 dichlorodimethydiphenyl disilizane in xylene. The reaction is carried out at about 40C for about 10 minutes.
EX~IPLE 10 Example 2 is repeated, except that the organometallic composition i5 a lO~o solution of 1,7 dichlorooctamethyl 33 ~6~
tetrasilizane in xylene. The reaction is carried out at about 40C for abouk 10 rninutes.
EXA;~IPLE 11 Example 2 is repeated, except ~hat the organometallic composition is a 10% solution of M-methylaminopropyl trimethyoxysilane in xylene. The reaction is carried out at about 40C for about lO minutes.
E~ IPLE 12 Example 2 is repeated, except that the organometalLic composition is a 10~ solution of 3-aminopropylmethyl diethoxy silane in xylene. The reaction is carried out at about 40~C for about 10 minutes~
EX~PLE 13 Example 2 is repeated, except that the organorr,etallic composition is a 10% solution of 1,3 divinyltetraethoxy disiloxane in xylene. The reaction is carried out at about 40C for about 10 minutes.
EXP~PLE 14 Example 2 is repeated, except that the organometallic composition is a 10% solution of ~-2 aminoethyl-3-aminopropyl trimethoxysilane in xylene. The reaction is carried out at about 40C for about 10 minutes.
E~IPLE 15 Example 2 is repeated, except that the organometallic composition is a 10% solution of 1,3 bis (gamma-arninopropyl) tetramethyl disiloxane in :~ylene. The reaction is carried out at about 40C for about 10 minutes.
EX~u~IPLE 16 Example 2 is repeated, except that the organometallic composition is a 10~ solution of tetraethyoxytitanium in xylene. The reaction is carried out at about room temperature for about 60 seconds.
EX~PLE_17 Example 16 is repeated, except that the organometallic composition is tetraethyoxytitanium. The reaction is carried out at about room temperature for about 30 seconds.
EXP~IPLE 18 Example 2 is repeated, except that the organometallic composition is a 10% solution of tetrabutoxytitanium in xylene. The reaction is carried out at about room temperature for about 60 seconds.
Example 18 is repeated, except that the organometallic composition is tetrabutoxytitanium. The reaction is carried out at about room temperature for about 30 seconds.
Y0984-lOI
si si I ~ \ / \ ~I
wherein each R and RI, individually, is H, alkyl, S cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually is H, alkyl or aryl; and X is 0, Si, or N-R"~
R \ ¦ / R
Si N - Si rI / ~
\ Si ~ N ~
RI / \ m ' R RI
14 3 ~ 4B
wherein each R ana RI, individuall,~, is ~, alkyl, cycloal~yl, aryl, halo, halo-suhstituted alkyl, or halo-substituted aryl; each ~II, individually, is H, al~yl, or aryl; and m is a whole nul~er integer >1 and prererahly 1 or 2.
~ \ I N I RII RRII
RII ~ ~ ~\ RrI 4.
N-R N-R N R
~I I I 1I I ,~ R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and each RII, individually, is H, alkyl, or aryl.
RII R R RII R
R
T~5i- N - Si t-O - S )p O - Si - N - Si \
R - ~ N-R R - N N R 5 R ~ R R \ I I ",R
~1 ~ Si I Sl I I~ N - Si wherein each R and RI, individually, is H, alkyl, Y09~4-1~1 cycloalkyl, aryl, halo, halo-substituted alkyl, cr halo-substituted aryl; each RII, individually, is ~, alXyl, or aryl; and p is a whole number in~eger of >1 and preferably 1-~o R R RII R RII RI
/ N ~ i N ( S N )r Si ~ 6 wherein each R and RI, individually, is H, aLkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually, is H, alkyl, or aryl; and r is a whole number integer of 0-102, preferably 1-4.
R R
R li ( CH2 )5 - --7 Si - RI
H- 1~ N '. 7-l R
R - ~i ( CH~ ;i /
R L
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and each s, individually, is a whole nu~ber integer >l, and preferably 1 or 2.
Y~984-lOl R Sl ¦ ~ Si ~ 8-H --N M - ~
\ I i XI - si wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo-substituted aryl, or halo; and XI is (-CH2-)t, or ~ y ~
wherein t is a whole number integer of >1 and preferably 1-4; and Y is 0, NH, or S.
wherein each R and R , individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl; and v is a wnole number integer of >1 and preferably 1-4.
17 ~ 8 ~c C 1 o .
~h - T 7I I I Ph N ~ N R N ---= --=~J
wherein each R anc RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl.
O R RIII
RTII C - N - Si ' - C RTII 11 wherein~each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-su~stituted alkyl, or halo-substituted aryl, and each RIII, individually, is alkyl.
\ Si/- R
H j l l R ~ / H 12.
~ : / N - Si ~ - N - S ~ RII
~wherein each R and RI, individually, is H, alkyl, ~ ,~
: ; :
Y0984-10l ~, : ~ :
::
:~:
cycloalkyl, ar~yl, halo, halo-substituted alkyl, or halo-substituted aryl; each RII, individually, is H, al'~yl, or aryl; and w is a whole nu~ber integer >1 and preferably 1-4.
~ H
/c2~
H C f i -_ N - Si CH
2 7-H NH 13.
2~ Ti fH
H C -CH H2C - CH ~
wherein z is a whole number integer of 0-4 and prererably 0-2.
r~S~ \
R O
wherein R is H, alkyl, cycloalkyl, aryl, halo, halo-substltuted alkyl, or halo-substituted aryl.
Y0984-lOI
1 9 ~.~6~
R \ / ~
R \ N3 15.
wherein each R and RI, individualLy, is H, alkyl, cycloalkyl, aryl, halo, halo-substituted alkyl, or halo-substituted aryl.
H ~I H C H R H
L
wherein each R and RI is H, alkyl, aryl, cycloalkyl, halo, halo-substituted alkyl, or halo-substituted aryl; and a is a whole number integer >1 and preferably 1-4.
~ N ~i N ~ 17.
RI
wherein R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo, halo-substitu~ed alkyl, or halo-substituted aryL.
yI i _ ~I 18 wherein each yI~ individually, is _ N \ N _ j ~=N/ or --U ¦ , ara RI and R, individually, is H, alkyl, aryl, cycloalkyl, halo, halo-substituted alkyl, or halo substituted aryl.
19.
N - Si ~ N
wherein R and R , individually, i~ H, al~yl, cycloalkyl, S aryl, halo, halo-substituted alkyl, or halo-substituted ary1.
:~
RIV R RIV
~VI - C ~ i . N -- C - - RJI 20.
OSi(R )3 RI OSi(R )3 wherein R and RI, individually, is H, alkyl, aryl, cycloalkyl, halo, halo.~substituted akyl, or halo-substituted aryl; each RI , individually, is H or alkyl; each R , individually, is H or alkyl; and eah RVI, individually, is alkyl or CX3(X=F, Cl, Br, I).
R - f _~7 - Si - N - C RVI 21.
GSi(R )3 R ISi(R )3 wherein R and RI, individually, is H, alkyl, aryl, cycloalkyl, halo, halo-substituted akyl, or halo-substituted aryl; each RIV, each RV, individually, is H or alkyl; and each R , individually, is alkyl or CX3(X=F,Cl, Br, I).
O R O
RVII -CHN Si NHI - ---RVII 22.
1~
R
22 ~
wherein R and RI, individually, is H, alkyl, aryL, cycloalkyl, halo, halo-substituted akyl, or halo-substitutec~
aryl; and each R II, individually, is alkyl.
pIX
(~VIII)2N~ Si _N(pVIII) 23.
~I
wherein each RIX, individually, is alkyl; ana eacn RVIII~
S individually, is alkyl.
N RII 2~.
R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo or halo-substituted aryl; each RII, individually, is H, alkyl or aryl.
. RII ~ / \ N RII and 25.
H2C (CH2)a .
~ ~ Yo984-101 :::
dimers and polymers thereo~ wherein each R and RI, indi~Jidually, ls H, alkyl, cycloalkyl, aryl, halo-substituted alkyl, halo, or halo-subs~ituted aryl, each R I, individually, is H, alkyl or aryl; and a is 1, 2, or 3.
~ (R \
R ~I~ RI ~6-wherein b is a whole number integer of 1-5; each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyL, halo, or halo-substituted aryl; each X, individually, is halo, SH, OH, ORX, and NH and Rx is alkyl, 1-5 carbon atoms, and preferably ethyl or methyl.
R \ RI
(R)3 - Si - N < / Si (R)3 27.
/Sl R R
wherein each R and RI, individually, is H, alkyl, cycloalkyl, aryl, halo-substituted alkyl r halo, or halo-substituted aryl.
Examples of suitable alkyl groups in the above formulas are ~ alkyl groups containing 1-12 carbon atoms and preferably 1-4 carbon atoms. Specific examples of such are methyl, ethyl, propyl, butyl, and octyl. The most preferred alky groups are methyl and ethyl.
Y098b- 101 ' ~;~mples of suit~ble c~clo~l~yl groups are cyclohe~l an~
cycloheptyl.
E~amples of suitable aryl groups are phenyl, tol~l, xylyl, and napthyl radicals.
Examples of suitable halo radicals are F, Cl, Br, and I.
E~amples of suitable halo-substituted alkyl groups are l,l,l-trifluoropropyl, and chloromethyl.
Examples of suitable halo-substituted aryl groups are chlorophenyl and dibromophenyl.
In many applications of the use of the products of the present invention, it is preferred that the orsanometallic compound not include any halogen component such as chlorine to assure against the possibiLity of causing corrosion due to the potential formation of some corrosive halide gas.
The preferred organometallic compounds are the cyclic organo silicon compounds and more preferably hexamethylcyclotri-silazane.
The amount of the organometallic material employed must be sufficient to provide the desired degree of cross-linking and plasma resistance. Usually, the relative amount of the organometallic material to the polymeric material provides at least about 1 part by weight of the metallic component (e.g. - Si) per 20 parts of the polymeric material, and up to about 1 part by weight of the metallic component per 2 25 parts by weight of the polymeric material, and preferably about 1 part by weight of the metallic component per 15 parts of the pol~meric material to about 1 part by weight of the metaliic component per 4 parts by weight of the Y09~4-lOl l polymeric material.
The cross--linked polymeric materials prepare~ in accordance with the present invention are resistant to oxygen plasma and are extremely stable when exposed to elevated temperatures. The cross-linked polymeric materials of the present invention are at least about 20 times, preferably at least about 50 times, and in many cases, at least about 100 times as resistant to oxygen plasma as is the corresponding noncross-linked polymeric material. Cross-linked polymeric materials, such as novolak resins in accordance with the present invention have thermal stabilities of up to about 400C; whereas, polymeric materials prepared with monofunctional organometallic materials, such as discussed in aforementioned ~.S. Patent 4,552,883, do not have thermal stabilities above about 200C.
Moreover, even upon decomposition, the cross-linked materials of the present invention, and particularly the novolak resins, do not form volatile materials at temperatures up to about 400C as occur when monofunctional organometallic compounds are employed in the reaction. The materials of the present invention exhibit good solvent resistance. Accordingly, materials of the present invention are useful in environments other than those which involve exposure to an oxygen-containing plasma. For instance, materials of the present invention can be used in applications which require materials to be resistant to high temperature.
The materials of the present invention can be prepared by reacting the polymeric material with the multifunctional organometallic material in either the vapor phase or preferably dissolved in a suitable solvent. In the preferred aspects of the present invention, the polymeric material is already in the form of a film or layer when contacted with the multifunctional organometallic material.
YO9-84~101 For instance, th~ pol~meric r~aterial, particularl~ ,/hen it is to be employed in a lithoyraphic process, is applied to a desired substrate to provide films generally about 1500 angstroms to about l mil thick, such as by spraying, spinning, dipping, or any o-ther known means of application of coating. Some suitable substrates include those Ised in the fabrication of semiconduc~or devices or integrat2d circuits whlch include wafers or chips overcoated with oxides and nitrides (silicon oxide and/or silicon nitride for diffusion masks and passivation) and/or metals normally employed in the metallization steps ror forming contacts anc conductor patterns on the semiconductor chip.
~loreover, the polymeric materials can be used as coatings on those substrates employed as chip encapsulants and including ceramic substrates and, especially, multilayer ceramic devices. Also included are dielectric substrates which can be thermoplastic and/or thermosetting polymers.
Typical thermosetting polymeric materials includ2 epoxv, phenolic-base materials, polyamides, and polyimides. The dielectric materials can be molded articles of the polymers containing fillers and/or reinforcing agents, such as glass-filled epoxy or phenolic-base materials. Examples of some phenolic-type materials include copolymers or phenol r resorcinol, and cresol. Examples of some suitable thermoplastic polymeric materials include polyolefins, such as polypropylene, polysulfones, polycarbonates, nitrile rubbers, and ABS polymers.
The reaction bet~een the organometallic material is usually carried out in about 5 minutes to about l hour depending upon the relative reactivities of the materials employea, the solvent system employed, and the depth through the film to which it is desired to cause the cross-linking. ~or instance, it may be desired to onl~ effect the reaction through a portion of the la~er of the pol~meric materi~l.
In most applications, at least about 25~, and preferably at least 50% of the total thickness of the film is cross-linked. In many instances, the entire thickness, or at least substantially -the entire film thickness, is cross-linked. ~sually the thickness reacted is at least 0.3 microns. Generally thicknesses above about 25 microns are not necessary for the applications to which the films are most useful. Preferably thickness is about 0.4 to about 10 microns. Most preferably the thickness is about 0.5 to about 5 microns.
In the preferred aspects of the present invention, the organometallic material is dissolved in an organic solvent which is non-reactive with the organometallic material. It is preferred that the inert organic solvent be aprotic. ~he most preferred solvents are the aromatic hydrocarbons and substituted aromatic hydrocarbons including benzene, toluene, xylene, and chlorobenzene. Other solvents include N-methyl pyrrolidone; y-butyrolactone; acetates , such as butyl acetate and 2-methoxy acetate; ethers; and tetrahydrofuran. In addition, the solvent is preferably selected so that it has some ability to diffuse enough through the polymeric material to provide the needed contact between the organometallic material and polymeric material.
It is preferred that this solvent be only a partial rather than a good solvent for the polymeric material. Accordingly, the choice of the polymeric material will have some effect upon the choice of the solvent used for best results.
In the preferred aspects of the present invention, the solvent component also includes a solvent in which the polymerlc material is readily soluble in when the major portion of the solvent component is a non solvent or only a Y09~4-101 2 ~
par~ial so1~ent ~or the pol~merlc rnaterial. The solvent for the ~ol~meric material is employed in arnoun~s effec~ive to decrease the necessary reaction time between the multifunctional organometallic material and the polymeric material. The solvent for the polymeric material must be non-reactive with the multifunctional oryanometallic material. Examples of suitable solvents for the pol~meric material to be employed are N-meth~l pyrrolidone y-butyrolactone and acetates such as cellosolve acetate, butyl acetate, a~d 2-methoxy ethyl acetate.
The solvent for the polymeric material is employed in relatively minor amounts so as not to remove or dissolve the polymeric film. Preferred amounts of the organic solvent for the polymeric material are about .01% to about 25~ by volume, and more preferably about 0.25~ to about 5~, based on the total amount of organic solvent in the liquid composition. The total amount of solvent in the liquid composition is usuall~ about 75% to about 98~ and preferably about 95~ to about 96% based upon the total of the solvent and organometallic material in the liquid composition. Use of elevated temperatures also enhances the diffusion through the polymeric material.
An example of a process employing the materials of the present invention involves coating a thin layer of about 0.
to about 10 microns of a photoresist material over a polymeric surface as the substrate. Examples of suitable photoresist materials include the above-described phenolic-formaldehyde photoresist containing quinone sensitizers.
Such materiais are preferably subjected to elevated temperatures of about 80C ror about 15 minutes to effect a precuring or prebake of the composition.
Y0984~
2 g The reslst is then e~posed to ultraviGlet Light and ~eveloped ln an ~lkaline soLution to remove those por~ions of the resist whlch were exposed to the ultraviolet light.
Next, the developed patterned images are contacted with the organometallic materials, such as by flooding the substrate on a spinner in a solution of the organometallic material solu-tion for about 1 minu~e to about 60 minutes.
The composite is then washed in a solvent, such as xylene, and baked at about 125C for about 1 hour.
Next, the composite is placed in a reaction chamber which is then evacuated and filled with oxygen. The pressure in the reaction chamber is about 10 millitorr and the gas is introduced into the reaction chamber at a flow rate of about 0.02 standard liters per minute. A plasma is formed in the oxygen gas by coupling radio frequency power of about 0.02 kilowatts to the plasma and is continued for about 10-250 minutes. The oxygen-containing plasma can be from oxygen, oxygen-inert gas mixtures (e.g. - argon), oxygen-halocarbon mixtures (e.g. - CF4), and oxygen-hydrocarbon, as is well-known.
~he portion of the organic polymeric substrate which is protected by the reaction product resists the o~ygen plasma and remains intact. That portion of the organic polymeric substrate not protected by the reaction proauct is etched by the oxyqen plasma.
The following non-limiting e~amples are presented to further illustrate the present invention.
E~ lPLE 1 A layer of about 1 micron thlck of Shipley ~Z-1350 positive photoresist, which is an m-cr2sol formaldehyde novolak polymer containing about 15~ by weight of 2-diazo-1-naphthoquinone-5-sulphonic acid ester, is coat~d onto a substrate ot a polyimide of about 2 microns thick.
The photoresist is prebaked at about 80C for about 15 minutes.
The resist is then imagewise exposed to ultrzviolet light and developed in an alkaline solution to remove those portions of the resist which were exposed to the ultraviolet light.
Next, the developed patterned image is reacted with hexamethylcyclotrisilazane by flooding the substrate on a spinner in a solution o~ 30% hexamethylcyclotrisilazane in chlorobenzene for about 10 minutes at room temperature.
The composite is then washed in xylene and baked at about 80C for about l hour.
Next, the composite is placed in a reaction chamber which is then evacuated and filied with oxygen. The pressure in the reaction chamber is about lO millitorr and the gas is introduced into the reaction chamber at a flow rate of about 0.02 standard liters per minute. The oxygen is disassociated by coupling radio frequency power of about 25 0.02 kilo~atts to the plasma and is continued for about 15 minutes.
The portion of the substrate which is protected by the reaction product resists the oxygen plasma and remains *Tr~ade Mark i$~4~
r 31 intact. That portion of the substrate not protectea ~y th reaction product is etched bv the oxygen plasma.
E,YAi~PLE 2 Example 1 is repeated, except that the organome~allic composition is a 10~ solution of hexamethylcyclotrisilazane in xylene. The reaction of the hexamethylcyclotrisilazane with the polymeric material is carried out at about 40C for about 30 minutes.
EX~MPLE 3 Example 2 is repeated, except that the organometallic composition is a 10% solution of hexamethylcyclotrisilazane in xylene containing 1~ by weight of N-methylpyrrolidone.
The reaction time is reduced to only 10 minutes.
E~AMPLE 4 Example 2 is repeated, except that the organometallic composition is a 10~ solution of hexamethylcyclotrisilazane in xylene containing 1% of y-butyrolactone. The reaction time between the silazane and polymeric material is reduced to 10 minutes.
A comparison of Examples 3 and 4 with Example 2 illustrates the improved results obtained by incorporating small amounts of a solvent for the polymeric material.
E'~AMPLE 5 Example 2 is repeated, except that the polymeric material is Kodak~820 positive resist. The reaction is carried out at about 75~C in about 45 minutes.
*Trade Mark ~Y0984-lOI
1~6~
EX~ PLE 6 .
Example 2 is repeated, except that the organometaLlic composition is a 10o solution of hexamethylcyclotrisilazane in xylene containing 5% by weight o~ rl-methylpyrrolidone and the polymeric material is Kodak 820 positive resist. The reaction is carried out at about 40C in about 10 minutes.
Example 2 is repeated, except that the organometallic composition is a 10% solution of hexamethlycyclotrisilazane in y-butyrolactone and the polymeric material is a terpolymer of methylmethacr~late, methacrylic acid, and methacrylic anhydride. The reaction is carried out at about 40C in about 10 minutes.
EXA~IPLE 8 Example 2 is repeated, except that the organometallic composition is a 10% solution of octamethylcyclotetrasili-zane in xylene. The reaction is carried out at about 40C
for about 10 minutes.
Example 2 is repeated, except that the organometallic composition is a 10% solution of 1,3 dichlorodimethydiphenyl disilizane in xylene. The reaction is carried out at about 40C for about 10 minutes.
EX~IPLE 10 Example 2 is repeated, except that the organometallic composition i5 a lO~o solution of 1,7 dichlorooctamethyl 33 ~6~
tetrasilizane in xylene. The reaction is carried out at about 40C for abouk 10 rninutes.
EXA;~IPLE 11 Example 2 is repeated, except ~hat the organometallic composition is a 10% solution of M-methylaminopropyl trimethyoxysilane in xylene. The reaction is carried out at about 40C for about lO minutes.
E~ IPLE 12 Example 2 is repeated, except that the organometalLic composition is a 10~ solution of 3-aminopropylmethyl diethoxy silane in xylene. The reaction is carried out at about 40~C for about 10 minutes~
EX~PLE 13 Example 2 is repeated, except that the organorr,etallic composition is a 10% solution of 1,3 divinyltetraethoxy disiloxane in xylene. The reaction is carried out at about 40C for about 10 minutes.
EXP~PLE 14 Example 2 is repeated, except that the organometallic composition is a 10% solution of ~-2 aminoethyl-3-aminopropyl trimethoxysilane in xylene. The reaction is carried out at about 40C for about 10 minutes.
E~IPLE 15 Example 2 is repeated, except that the organometallic composition is a 10% solution of 1,3 bis (gamma-arninopropyl) tetramethyl disiloxane in :~ylene. The reaction is carried out at about 40C for about 10 minutes.
EX~u~IPLE 16 Example 2 is repeated, except that the organometallic composition is a 10~ solution of tetraethyoxytitanium in xylene. The reaction is carried out at about room temperature for about 60 seconds.
EX~PLE_17 Example 16 is repeated, except that the organometallic composition is tetraethyoxytitanium. The reaction is carried out at about room temperature for about 30 seconds.
EXP~IPLE 18 Example 2 is repeated, except that the organometallic composition is a 10% solution of tetrabutoxytitanium in xylene. The reaction is carried out at about room temperature for about 60 seconds.
Example 18 is repeated, except that the organometallic composition is tetrabutoxytitanium. The reaction is carried out at about room temperature for about 30 seconds.
Y0984-lOI
Claims (42)
1. A process which comprises:
providing a layer of polymeric material wherein said polymeric material contains at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups reacting at least a portion of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups or said polymeric material to thereby render the said at least portion of said layer resistant to oxygen plasma which is at least about 20 times greater than is the polymeric material before it is reacted with said organometallic material and then subjecting said layer to a gas plasma atmosphere.
providing a layer of polymeric material wherein said polymeric material contains at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups reacting at least a portion of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups or said polymeric material to thereby render the said at least portion of said layer resistant to oxygen plasma which is at least about 20 times greater than is the polymeric material before it is reacted with said organometallic material and then subjecting said layer to a gas plasma atmosphere.
2. The process of claim 1 wherein said gas plasma atmosphere is an oxygen-containing plasma atmosphere.
3. The process of claim 1 wherein the resistance to oxygen plasma is increased at least about 50 times, as compared to the polymeric material before it is reacted with the organometallic material.
4. The process of claim 1 wherein the increase in resistance to oxygen plasma is at least about 100 times that of the polymeric material before it is reacted with the organometallic material.
5. The process of claim 1 wherein at least about 25% of the thickness of the layer of polymeric material is reacted with the organometallic material.
6. The process of claim 1 wherein at least about 50% of the thickness of the layer of polymeric material is reacted with the organometallic material.
7. The process of claim 1 wherein at least substantially, the entire thickness of the layer of polymeric material is reacted with the organometallic material.
8. The process of claim 1 wherein said multifunctional organometallic material is provided as a liquid composition in a solvent for the organometallic material wherein the solvent is nonreactive with the organometallic material.
9. The process of claim 1 wherein that portion of the layer which is reacted contains at least about 1 part by weight of the metallic component of the organometallic material per 20 parts of polymeric material.
10. The process of claim 9 wherein that portion of the layer which is reacted contains up to 1 part by weight of the metallic component of the organometallic material per 2 parts by weight of the polymeric material.
11. The process of claim 1 wherein that portion of the layer which is reacted contains a ratio of a metallic component of the organometallic material to the polymeric material of about 1:15 to about 1:4.
12. The process of claim 1 wherein said organometallic material is an organosilicon material.
13. The process of claim 1 wherein said organometallic material is a cyclic organosilicon compound.
14. The process of claim 1 wherein said organometallic material is hexamethylcyclotrisilazane.
15. The process of claim 1 wherein said layer is about 0.4 to about 10 microns thick.
16. A process which comprises providing a layer of polymeric material on a substrate wherein said polymeric material contains at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups reacting at least through 25% of the depth of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups of said polymeric material.
17. The process of claim 16 wherein at least 50% of the thickness of said layer is reacted.
18. The process of claim 16 wherein the entire thickness of said layer is reacted.
19. The process of claim 16 wherein said thickness is at least about 0.3 microns.
20. The process of claim 16 wherein said thickness is about 0.3 to 25 microns.
21. The process of claim 16 wherein said thickness is about 0.5 to about 5 microns.
22. The process of claim 15 wherein said layer is prebaked prior to reacting.
23. The process of claim 1 wherein said polymeric material is a prepolymerized phenolic-formaldehyde polymer containing a diazo ketone sensitizer.
24. A process for rendering a polymeric material resistant to oxygen plasma which comprises:
providing a polymeric material containing at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups;
providing a liquid composition containing a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive functional groups of said polymeric material, a solvent for said multifunctional organometallic material wherein said solvent is nonreactive with said organometallic material, and a solvent for said polymeric material in an amount effective to decrease the reaction time between said multifunctional organometallic material and said polymeric material, and wherein said solvent for said polymeric material is not reactive with said multifunctional organometallic material; and contacting said liquid composition with said polymeric material to thereby render said polymeric material resistant to oxygen plasma.
providing a polymeric material containing at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups;
providing a liquid composition containing a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive functional groups of said polymeric material, a solvent for said multifunctional organometallic material wherein said solvent is nonreactive with said organometallic material, and a solvent for said polymeric material in an amount effective to decrease the reaction time between said multifunctional organometallic material and said polymeric material, and wherein said solvent for said polymeric material is not reactive with said multifunctional organometallic material; and contacting said liquid composition with said polymeric material to thereby render said polymeric material resistant to oxygen plasma.
25. The process of claim 24 wherein said organometallic material is hexamethylcyclotrisilazane.
26. The process of claim 24 wherein said polymeric material is a phenolic-formaldehyde polymer.
27. The process of claim 24 wherein said organic solvent for the polymeric material is present in an amount of about 0.01 to about 25% by volume based on the total amount of organic solvent.
28. The process of claim 24 wherein said organic solvent for the polymeric material is present in an amount of about 0.25 to about 5% by volume based upon the total amount of organic solvent in the composition.
29. The process of claim 24 wherein said polymeric material is in the form of a layer.
30. The process of claim 24 wherein said solvent for the multifunctional organometallic material is an aromatic hydrocarbon or substituted aromatic hydrocarbon.
31. The process of claim 24 wherein said organometallic composition is a solution of hexamethylcyclotrisilazane in xylene containing a solvent for the polymeric material selected from the group of N-methylpyrrolidone and .gamma.-butyrolactone.
32. The process of claim 31 wherein said polymeric material is a phenolic-formaldehyde polymer.
33. A cross-linked polymeric material being the reaction product of a cyclic organometallic material hving 4, 5 or 6 atoms in the ring and a polymeric material containing reactive hydrogen functional groups, or reactive hydrogen functional precursor groups, or both.
34. The cross-linked polymeric material of claim 33 wherein said polymeric material is a phenolic-formaldehyde polymer.
35. The polymeric material of claim 33 wherein said organometallic material is hexamethylcyclotrisilazane.
36. The cross-linked polymeric material of claim 35 which contains at least about 1 part by weight of silicon per 20 parts of the polymeric material.
37. The cross-linked polymeric material or claim 35 which contains up to about 1 part by weight of silicon per 2 parts by weight of the polymeric material.
38. The polymeric material of claim 35 wherein the ratio of silicon to polymeric material is about 1:15 to about 1:4.
39. The cross-linked polymeric material of claim 33 which is in the form of a layer.
40. The cross-linked polymeric material of claim 33 which is in the form of a layer of about 0.4 to about 10 microns thick.
41. The polymeric material of claim 33 wherein said organometallic material is a cyclic organometallic material.
42. A process which comprises:
providing a layer of polymeric material wherein said polymeric material contains at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups; reacting at least a portion of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups of said polymeric material to thereby render the said at least portion of said layer more resistant to oxygen plasma than was the polymeric material before it was reacted with said organometallic material.
providing a layer of polymeric material wherein said polymeric material contains at least reactive hydrogen functional groups or reactive hydrogen functional precursor groups; reacting at least a portion of said layer of polymeric material with a multifunctional organometallic material containing at least two functional groups which are reactive with the reactive groups of said polymeric material to thereby render the said at least portion of said layer more resistant to oxygen plasma than was the polymeric material before it was reacted with said organometallic material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/713,509 US4782008A (en) | 1985-03-19 | 1985-03-19 | Plasma-resistant polymeric material, preparation thereof, and use thereof |
| US713,509 | 1985-03-19 |
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| CA1266148A true CA1266148A (en) | 1990-02-20 |
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| CA000499386A Expired - Fee Related CA1266148A (en) | 1985-03-19 | 1986-01-10 | Plasma-resistant polymeric material, preparation thereof, and use thereof |
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| US (1) | US4782008A (en) |
| EP (1) | EP0198215B1 (en) |
| JP (1) | JPS61219034A (en) |
| AU (2) | AU576049B2 (en) |
| BR (1) | BR8600996A (en) |
| CA (1) | CA1266148A (en) |
| DE (1) | DE3679434D1 (en) |
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| US4289473A (en) * | 1980-01-04 | 1981-09-15 | Holdt J W Von | Mold gate permitting the introduction of stiff molding compound into a mold chamber |
| US4307178A (en) * | 1980-04-30 | 1981-12-22 | International Business Machines Corporation | Plasma develoment of resists |
| JPS57139585A (en) * | 1981-02-13 | 1982-08-28 | Kao Corp | Color concentrating agent |
| JPS57157241A (en) * | 1981-03-25 | 1982-09-28 | Oki Electric Ind Co Ltd | Formation of resist material and its pattern |
| US4396704A (en) * | 1981-04-22 | 1983-08-02 | Bell Telephone Laboratories, Incorporated | Solid state devices produced by organometallic plasma developed resists |
| JPS57202535A (en) * | 1981-06-09 | 1982-12-11 | Fujitsu Ltd | Formation of negative resist pattern |
| JPS57202533A (en) * | 1981-06-09 | 1982-12-11 | Fujitsu Ltd | Formation of pattern |
| EP0091651B1 (en) * | 1982-04-12 | 1988-08-03 | Nippon Telegraph And Telephone Corporation | Method for forming micropattern |
| US4493855A (en) * | 1982-12-23 | 1985-01-15 | International Business Machines Corporation | Use of plasma polymerized organosilicon films in fabrication of lift-off masks |
| US4489200A (en) * | 1983-04-11 | 1984-12-18 | General Electric Company | One-component RTV silicone rubber compositions with good self-bonding properties to acrylate plastics |
| JPS59202636A (en) * | 1983-05-04 | 1984-11-16 | Hitachi Ltd | Formation of fine pattern |
| US4430153A (en) * | 1983-06-30 | 1984-02-07 | International Business Machines Corporation | Method of forming an RIE etch barrier by in situ conversion of a silicon containing alkyl polyamide/polyimide |
| CA1248402A (en) * | 1983-09-16 | 1989-01-10 | Larry E. Stillwagon | Method of making articles using gas functionalized plasma developed layer |
| US4507331A (en) * | 1983-12-12 | 1985-03-26 | International Business Machines Corporation | Dry process for forming positive tone micro patterns |
| GB8403698D0 (en) * | 1984-02-13 | 1984-03-14 | British Telecomm | Semiconductor device fabrication |
| US4552833A (en) * | 1984-05-14 | 1985-11-12 | International Business Machines Corporation | Radiation sensitive and oxygen plasma developable resist |
| US4521274A (en) * | 1984-05-24 | 1985-06-04 | At&T Bell Laboratories | Bilevel resist |
| JPS6129214A (en) * | 1984-07-19 | 1986-02-10 | Nec Corp | Current feedback type transistor driving circuit |
| GB8427149D0 (en) * | 1984-10-26 | 1984-12-05 | Ucb Sa | Resist materials |
| CA1267378A (en) * | 1984-12-07 | 1990-04-03 | Jer-Ming Yang | Top imaged and organosilicon treated polymer layer developable with plasma |
| US4551418A (en) * | 1985-02-19 | 1985-11-05 | International Business Machines Corporation | Process for preparing negative relief images with cationic photopolymerization |
| US4782008A (en) * | 1985-03-19 | 1988-11-01 | International Business Machines Corporation | Plasma-resistant polymeric material, preparation thereof, and use thereof |
-
1985
- 1985-03-19 US US06/713,509 patent/US4782008A/en not_active Expired - Fee Related
- 1985-12-24 JP JP60289538A patent/JPS61219034A/en active Pending
-
1986
- 1986-01-10 CA CA000499386A patent/CA1266148A/en not_active Expired - Fee Related
- 1986-01-22 AU AU52605/86A patent/AU576049B2/en not_active Ceased
- 1986-03-07 BR BR8600996A patent/BR8600996A/en not_active Application Discontinuation
- 1986-03-11 EP EP86103208A patent/EP0198215B1/en not_active Expired
- 1986-03-11 DE DE8686103208T patent/DE3679434D1/en not_active Expired - Fee Related
-
1988
- 1988-07-28 AU AU20125/88A patent/AU595127B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| AU576049B2 (en) | 1988-08-11 |
| EP0198215A2 (en) | 1986-10-22 |
| AU595127B2 (en) | 1990-03-22 |
| EP0198215A3 (en) | 1988-09-21 |
| US4782008A (en) | 1988-11-01 |
| AU5260586A (en) | 1986-09-25 |
| DE3679434D1 (en) | 1991-07-04 |
| EP0198215B1 (en) | 1991-05-29 |
| BR8600996A (en) | 1986-11-18 |
| JPS61219034A (en) | 1986-09-29 |
| AU2012588A (en) | 1988-11-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |