CA1320300C - Photopatternable silicone polyamic acid, method of making and use - Google Patents
Photopatternable silicone polyamic acid, method of making and useInfo
- Publication number
- CA1320300C CA1320300C CA000565353A CA565353A CA1320300C CA 1320300 C CA1320300 C CA 1320300C CA 000565353 A CA000565353 A CA 000565353A CA 565353 A CA565353 A CA 565353A CA 1320300 C CA1320300 C CA 1320300C
- Authority
- CA
- Canada
- Prior art keywords
- polyamic acid
- silicone
- silicone polyamic
- patterned
- photoresist
- 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.)
- Expired - Fee Related
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
- H01L21/0276—Photolithographic processes using an anti-reflective coating
Abstract
RD-17,379 use of such silicone polyamic acid, as compared to "Pyralin"
polyamic acid, it was found that the problem of premature imidization also occurred during the drying of the applied silicone polyamic acid prior to the spin coating of the photoresist. The work-life of the silicone polyamic acid as well as its usefulness during the development of the applied photoresist also was unsatisfactory.
The present invention is based on the discovery that certain silicone polyamic acids, resulting from the use of a siloxane containing norbornane bisanhydride (DiSiAn), shown by Ryang U.S. patent 4,381,396, assigned to the same assignee as the present invention, in combination with benzophenone dianhydride (BTADA) and aryldiamine, have been found to resist excessive imidization during the initial drying step of the silicone polyamic acid after its application to a substrate.
Temperatures up to 125°C for a period of 60 minutes can be used to make tack-free silicone polyamic acids which can be readily patterned during the development of a photopatterned photoresist. Surprisingly, the patterned silicone polyamic acid thereafter can be readily removed if used as an antireflective coating. The patterned silicone polyamic acid also can be fully imidized, rendering it substantially insoluble in conventional organic solvents, such as N-methylpyrrolidone in instances where it is used to make a color filter.
STATEMENT OF THE INVENTION
There is provided by the present invention, a method for patterning adherent silicone polyamide acid on the surface of at least a portion of a substrate, where the silicone polyamic acid is patterned by
polyamic acid, it was found that the problem of premature imidization also occurred during the drying of the applied silicone polyamic acid prior to the spin coating of the photoresist. The work-life of the silicone polyamic acid as well as its usefulness during the development of the applied photoresist also was unsatisfactory.
The present invention is based on the discovery that certain silicone polyamic acids, resulting from the use of a siloxane containing norbornane bisanhydride (DiSiAn), shown by Ryang U.S. patent 4,381,396, assigned to the same assignee as the present invention, in combination with benzophenone dianhydride (BTADA) and aryldiamine, have been found to resist excessive imidization during the initial drying step of the silicone polyamic acid after its application to a substrate.
Temperatures up to 125°C for a period of 60 minutes can be used to make tack-free silicone polyamic acids which can be readily patterned during the development of a photopatterned photoresist. Surprisingly, the patterned silicone polyamic acid thereafter can be readily removed if used as an antireflective coating. The patterned silicone polyamic acid also can be fully imidized, rendering it substantially insoluble in conventional organic solvents, such as N-methylpyrrolidone in instances where it is used to make a color filter.
STATEMENT OF THE INVENTION
There is provided by the present invention, a method for patterning adherent silicone polyamide acid on the surface of at least a portion of a substrate, where the silicone polyamic acid is patterned by
Description
13203~ RD-17,379 PHOTOPATTERNAB~E SI~ICONE POLYAMIC ACID, METHOD OF MAKING AND USE
BACKGROUND OF THE INVENTIO~
The present invention relates to a silicone polyamic acid which can be photopatterned on various substrates such as glass, sil~con, or aluminum and a method ~or making such materials.- More particularly, the present invention relates to a photopatternable ~ilicone polyamic acid which can be used as an antireflective ~oating for patterning photoresists, or can be photopatterned on a transparent substrate such as silicon or glass and thereafter imidized to provide for the production of a color filter.
Prior to the present i~vention, polyamic acid solutions, such as "Pyralin"* polyamic acid, was used to coat various ~u~strates to thicknesses o about 2.5 microns by a ; standard spinning technique. The applied polyamic acid, a copolymer of pyromellitic dian~ydride and 4,4'-oxydianiline in N-methylpyrrolidone had to be refrigerated during storage at 4C maximum, or it readi}y converted ~o the insoluble imidized state. As a result, it was diicult to ~pin dry "Pyralin"* polyamic acid to a tack-free state, prior to applying a p~itive photoresist ~o its ~urace, followed by photopatterning and developing.
Improved polyamic acid photopatterning was achieved by utilizing a silicone polyamic acid, resulting from the intercondensation of benzophenone dianhydride and a polydiorganosiloxane having terminal aminoalkyl groups attached to silicon by silicon-carbon linkages. Although improved adhesion to silicon or glass was achieved with the *Tradem~rk a . ' -1-~2Q3~ 7 37g (1) spin coating a silicone polyamic acid onto the surface of the substrate, (2) drying the silicone polyamic acid at a temperature of at least 100C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned W light, and ~5) developing the resulting patterned silicone polyamic acid-photoresist composite, where the silicone polyamic acid is the intercondensation product of reaction of about 2% less than stoichiometric, to about stoichiometric, of aryldiamine and organic dianhydride, comprising a mixture of from about 20 to 80 mole percent of norbornane organosiloxane bisanhydride and from about 80 mole percent to about 20 mole percent of aromatic organic bisanhydride~ and preferably from about 30 to 70 mole percent of norbornane organosiloxane bisanhydride and from about 70 mole percent to 30 mole percent of aromatic organic bisanhydride based on the total moles of organic dianhydrid~.
In a further aspect of the present invention, there is provided a method for patterning adherent silicone-polyimide-onto the surface of a transparent substrate which comprises, (1) spin coating a silicone polyamic acid onto the surface of a transparent substrate, (2) drying the silicone polyamic acid at a temperature of at least 100C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, ~ 32~3~ RD-17,379 (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite, (6) stripping the photoresist from the surface of the silicone polyamic acid, and .(7) heaking the resulting patterned silicone polyamic acid until imidized, where ~he silicone polyamic acid is as previously defined.
In an additional aspect of the present invention, there is provided a photoimaging method for p~tterning a substrate, using n antireflective silicone-polyamic acid coating which comprises, (1) spin coating a silicone polyamic acid having an effective amount of an organic dye with a maximum absorption coefficient in the range of 200 nm to 450 nm, (2) drying the silicone polyamic acid at a temperature of at least 100C, ~3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite (6~ etching exposed substrate through the patterned silicone polyamic acid-photoresist composite, and (7) stripping the silicone polyamic acid-photoresist composite from the resulting etched substrate where the silicone-polyamic acid is as previously defined.
~32~3~ RD-17,379 The norbornane anhydride terminated organosiloxane which can be used in the practice o~ the present invention is shown by Ryang, U.S. Patents 4,381,396 and 4,404,350, assigned to the same assignee as the present invention.
For example, there can be used 5,5'-(1,1,3,3-tetramethyl-1,1,3-disiloxanediyl)-bisnorbornane-2,3-dicarboxylic anhydride.
Organic dianhydrides which can be used in combination with the above~described norbornane anhydride terminated organosiloxane are, for example, benzophenone dianhydride, pyromellitic dianhydride, oxybisphthalic anhydride, and tetracarboxybiphenyl dianhydride.
Organic diamines which can be used in the practice of the present inventio~ to make the afore-described silicone polyamic acid are, for example, m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
4,4'-diaminodiphenyl ether;
1,5-diaminonaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-diaminotoluene;
2,6-diaminotoluene;
2,4-diamino-t-butyl toluene;
1,3-diamino-4-isopropylbenzene;
1,2-bis(3-aminopropoxy)ethane;
m-xylylenediamine;
p-xylylenediamine;
~203~n RD-17,37g bis(4-aminocyclohexyl)methane;
decamethylenediamine;
3-methylheptamethylenediamine;
4,4-dimethylheptamethylenediamine;
2,11-dodecanediamine;
2,2-dimethylpropylenediamine;
octamethylenediamine;
3-methoxyhexamethylenediamine;
2,5-dimethylhexamethylenediamine;
2,5-dimethylheptamethylenediamine;
3-methylheptamethylenediamine;
5-methylnonamethylenediamine;
1,4-cyciohexanediamine;
1,15-octadecanediamine;
bis~3-aminopropyl)sulfide;
N-methyl-bis~3-aminopropyl)amine;
hexamethylenediamine;
heptamethylenediamine;
2,4-diaminotoluene;
nonamethylenediamine;
2,6-diaminotoluene;
bis-(3-aminopropyl)tetramethyldisiloxane, etc.
Another aspect of the present invention is directed to photopatternable silicone polyamic acid which contain from 2% to 40% by weight of compatible organic dye based on the weight of silicone polyamic acid and such compatible organic dye to provide for photopatterned tinted silicone polyimide. Eor example, there can be used in the practice of the present invention, silicone polyamic acid which can be combined with a green, red, blue or yellow dye to provide for the production of color filters useful for liguid crystal displays.
~ 32~300 RD-l7~37g A further aspect of the present invention is directed to a sillcone polyamic acid which contains a sufficient amount of an organic dye capable o~ absorbing in the 200 to 450 nm region to produce an antireflective surface effect during photoimagin~. Depending upon the absorption capacity and thickness of coating u~ed, the weight ~0 of the dye can vary. For example, there can be used 2% to 30% by weight of an absorbing dye such as coumarin based on the weight of silicone-polyamic acid.
Some of the organic dyes which can be utilized in the practice of the present invention in combination with the ~ilicone polyamic acid to make tinted silicone-polyimide are, for example, commercially available green dyes such as ~cid green 41, acid green ~5, Naphthol green B, red dyes such as chromotrope 2B, Direct red 81, and ~lue dyes such as a~id blue 80, Chicago sky blue, and ani}ine blu~.
A variety of the above acid dyes can be modified in accordance with the practice of the invention for use in polyamic acids. The sodium cations which are charac~eristic of the acid dyes can be replaced with a variety of onium cations, typically quaternary ammonium or phosphonium cations such as benzyltrimethylammonium, tetrabutylammonium, tetraethylammonium, and tetrabutylphosphonium. The modified dyes can be prepared hy extraction of an agueous slurry of the commercial acid dye with methylene chloride. The solvent can be stripped to obtain the modified dye in high yield. The modified dyes were found to be soluble in N-methylpyrrolidone, in polyamic acid films and in polyimide films. The visible spectra of the onium salt dyes were undistinguishable from the sodium cation dyes.
The silicone polyamic acid used in the practice of the present invention is preferably prepared by a two-step process from aryldiamine and mixtures of norbornane 132~3~ RD-17,379 anhydride terminated organosiloxane, hereinafter referred to as "DiSiAn" and organic aromatic dianhydride which is preferably benzophenone dianhydride or hereinafter "BTDA".
An intercondensation solution can be used having from 10% to 30% by weight solids in a dipolar aprotic solvent. Among the dipolar aprotic solvents which can be used in the practice of the method of the present invention to prepare the silicone polyamic acid, there are included N-methylpyrrolidone, N,N-dimethylformamide.
Preferably, N-methylpyrrolidone is used as the dipolar aprotic solvent. Preferably a two-step process can be used where the ratio of DiSiAn to BTDA can be varied.
The preferred procedure is to ensure incorporation of the less reactive DiSiAn with aryldiamine for 30-60 minutes at about 90 to 100C. Incorporation of the BTDA can then proceed. During intercondensation, the mixture can be agitated, such as by stirring. After dissolution of the BTDA, the solutio~ can be maintained at 100 to 110C for an additional hour.
If desired, from 2% to 30% by weight of a suitable organic dye which is compatible with the silicone polyamic acid can be added with stirring. The tinted polyamic acid can then be spread as a thin film at thicknesses of from 1 to 20 microns on a suitable transparent substrate such as glass, silicon substrate or thermoplastic, for example polymethylmethacrylate, 'ILexan''* polycarbonate, thereafter hea ed to a temperature in the range ~f from 100C to 125C
to effect the removal of excess organic solvent. When the dried polyamic acid film is substantially tack~free, a suitable positive photoresist or negative photoresist can be spin coated onto its surface. The photoresist can be applied to a thickness of about .5 to 2 microns. The resulting composite can then be heated at a temperature from *Trademark 1 32030~ RD-17,379 80C to 100C to effect the removal of excess solvent, such as water or inert organic solvent.
In a preferred procedure for maki~q the silicone polyamic acid, an excess of the aryldiamine is avoided to minimize the production of gelled particles which can adv~rsely alter the film characteristics of the resulting silicone polyamic acid and silicone polyimide.
A color filter can be prepared in accordance with the practice of the method of the present invention on a transparent substrate utilizing a step-wise procedure for applyin~ tinted silicone polyimide. For example, a transparent substrate can be initially patterned with transparent silicone polyamic acid, tinted red, in accordance with the aforedescribed procedure. The silicone polyamic acid can thereafter be imidized by heating to a temperature of 200C for 60 minutes. The red tinted silicone polyimide will transmit red light, which can be patterned on the transparent substrate as an array of sguares, 250 microns on each side. Areas free of tinted silicone polyimide will transmit white light. The sub~trate can then be treated with additional tinted silicone polyamic acid, for example blue tinted silicone polyamic acid, and the process repeated. By the proper choice of masks and tinted silicone polyamic acid, a color filt~r can be made Z5 capable of exclusively transmitting blue, green and red light.
The following examples are given by way of illustration an~ not by way of limitation. All parts are by weight.
A mixture of 3.7008 grams (8.00 millimoles) of 5,5'-(1,1,3,3 tetramethyl-1,1,3-disiloxanediyl)-bis-norbor-9 _ ~32Q3~ RD-17,379 nane-2,3-dicarboxylic anhydride (DiSiAn), 2.1412 grams (19.8 millimoles) of metaphenylenediamine (MPD), and 23 grams of N~methylpyrrolidone (NMP) was warmed with stirring to 60C
for 30 minutes to effect complete solution and the formation of a silicone polyamic acid. There was then added to the mixture 3.9326 grams (12.20 millimoles) of benzophenonedianhydride (BTDA), while the mixture was stirred to provide a molar proportion of 40:60 of DiSiAn to BTDA units in the mixture. The mixture was then heated with stirring to 80C and aliquots were withdrawn at 10-minute intervals. Approximately 5 mil thick films were drawn onto glass slides and dried at 100C for 30 minutes. Some of the film were baked an additional 30 minutes at 200C. The solubilities of the resulting films were then tested by immersing them in a 0.5% by weight of aqueous tetramethyl ammonium hydroxide or sodium hydroxide solution "aqueous caustic" and also by baking the films an additional 30 minutes at 200C followed by immersion in NMP to determine their solubility in NMP. The following results show the aqueous caustic and NMP solubilities of films obtained from aliquots of silicone polyamic acid withdrawn at 10-minute intervals over a period of from 0 to 120 minutes from the reaction mixture.
BACKGROUND OF THE INVENTIO~
The present invention relates to a silicone polyamic acid which can be photopatterned on various substrates such as glass, sil~con, or aluminum and a method ~or making such materials.- More particularly, the present invention relates to a photopatternable ~ilicone polyamic acid which can be used as an antireflective ~oating for patterning photoresists, or can be photopatterned on a transparent substrate such as silicon or glass and thereafter imidized to provide for the production of a color filter.
Prior to the present i~vention, polyamic acid solutions, such as "Pyralin"* polyamic acid, was used to coat various ~u~strates to thicknesses o about 2.5 microns by a ; standard spinning technique. The applied polyamic acid, a copolymer of pyromellitic dian~ydride and 4,4'-oxydianiline in N-methylpyrrolidone had to be refrigerated during storage at 4C maximum, or it readi}y converted ~o the insoluble imidized state. As a result, it was diicult to ~pin dry "Pyralin"* polyamic acid to a tack-free state, prior to applying a p~itive photoresist ~o its ~urace, followed by photopatterning and developing.
Improved polyamic acid photopatterning was achieved by utilizing a silicone polyamic acid, resulting from the intercondensation of benzophenone dianhydride and a polydiorganosiloxane having terminal aminoalkyl groups attached to silicon by silicon-carbon linkages. Although improved adhesion to silicon or glass was achieved with the *Tradem~rk a . ' -1-~2Q3~ 7 37g (1) spin coating a silicone polyamic acid onto the surface of the substrate, (2) drying the silicone polyamic acid at a temperature of at least 100C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned W light, and ~5) developing the resulting patterned silicone polyamic acid-photoresist composite, where the silicone polyamic acid is the intercondensation product of reaction of about 2% less than stoichiometric, to about stoichiometric, of aryldiamine and organic dianhydride, comprising a mixture of from about 20 to 80 mole percent of norbornane organosiloxane bisanhydride and from about 80 mole percent to about 20 mole percent of aromatic organic bisanhydride~ and preferably from about 30 to 70 mole percent of norbornane organosiloxane bisanhydride and from about 70 mole percent to 30 mole percent of aromatic organic bisanhydride based on the total moles of organic dianhydrid~.
In a further aspect of the present invention, there is provided a method for patterning adherent silicone-polyimide-onto the surface of a transparent substrate which comprises, (1) spin coating a silicone polyamic acid onto the surface of a transparent substrate, (2) drying the silicone polyamic acid at a temperature of at least 100C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, ~ 32~3~ RD-17,379 (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite, (6) stripping the photoresist from the surface of the silicone polyamic acid, and .(7) heaking the resulting patterned silicone polyamic acid until imidized, where ~he silicone polyamic acid is as previously defined.
In an additional aspect of the present invention, there is provided a photoimaging method for p~tterning a substrate, using n antireflective silicone-polyamic acid coating which comprises, (1) spin coating a silicone polyamic acid having an effective amount of an organic dye with a maximum absorption coefficient in the range of 200 nm to 450 nm, (2) drying the silicone polyamic acid at a temperature of at least 100C, ~3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite (6~ etching exposed substrate through the patterned silicone polyamic acid-photoresist composite, and (7) stripping the silicone polyamic acid-photoresist composite from the resulting etched substrate where the silicone-polyamic acid is as previously defined.
~32~3~ RD-17,379 The norbornane anhydride terminated organosiloxane which can be used in the practice o~ the present invention is shown by Ryang, U.S. Patents 4,381,396 and 4,404,350, assigned to the same assignee as the present invention.
For example, there can be used 5,5'-(1,1,3,3-tetramethyl-1,1,3-disiloxanediyl)-bisnorbornane-2,3-dicarboxylic anhydride.
Organic dianhydrides which can be used in combination with the above~described norbornane anhydride terminated organosiloxane are, for example, benzophenone dianhydride, pyromellitic dianhydride, oxybisphthalic anhydride, and tetracarboxybiphenyl dianhydride.
Organic diamines which can be used in the practice of the present inventio~ to make the afore-described silicone polyamic acid are, for example, m-phenylenediamine;
p-phenylenediamine;
4,4'-diaminodiphenylpropane;
4,4'-diaminodiphenylmethane;
benzidine;
4,4'-diaminodiphenyl sulfide;
4,4'-diaminodiphenyl sulfone;
4,4'-diaminodiphenyl ether;
1,5-diaminonaphthalene;
3,3'-dimethylbenzidine;
3,3'-dimethoxybenzidine;
2,4-diaminotoluene;
2,6-diaminotoluene;
2,4-diamino-t-butyl toluene;
1,3-diamino-4-isopropylbenzene;
1,2-bis(3-aminopropoxy)ethane;
m-xylylenediamine;
p-xylylenediamine;
~203~n RD-17,37g bis(4-aminocyclohexyl)methane;
decamethylenediamine;
3-methylheptamethylenediamine;
4,4-dimethylheptamethylenediamine;
2,11-dodecanediamine;
2,2-dimethylpropylenediamine;
octamethylenediamine;
3-methoxyhexamethylenediamine;
2,5-dimethylhexamethylenediamine;
2,5-dimethylheptamethylenediamine;
3-methylheptamethylenediamine;
5-methylnonamethylenediamine;
1,4-cyciohexanediamine;
1,15-octadecanediamine;
bis~3-aminopropyl)sulfide;
N-methyl-bis~3-aminopropyl)amine;
hexamethylenediamine;
heptamethylenediamine;
2,4-diaminotoluene;
nonamethylenediamine;
2,6-diaminotoluene;
bis-(3-aminopropyl)tetramethyldisiloxane, etc.
Another aspect of the present invention is directed to photopatternable silicone polyamic acid which contain from 2% to 40% by weight of compatible organic dye based on the weight of silicone polyamic acid and such compatible organic dye to provide for photopatterned tinted silicone polyimide. Eor example, there can be used in the practice of the present invention, silicone polyamic acid which can be combined with a green, red, blue or yellow dye to provide for the production of color filters useful for liguid crystal displays.
~ 32~300 RD-l7~37g A further aspect of the present invention is directed to a sillcone polyamic acid which contains a sufficient amount of an organic dye capable o~ absorbing in the 200 to 450 nm region to produce an antireflective surface effect during photoimagin~. Depending upon the absorption capacity and thickness of coating u~ed, the weight ~0 of the dye can vary. For example, there can be used 2% to 30% by weight of an absorbing dye such as coumarin based on the weight of silicone-polyamic acid.
Some of the organic dyes which can be utilized in the practice of the present invention in combination with the ~ilicone polyamic acid to make tinted silicone-polyimide are, for example, commercially available green dyes such as ~cid green 41, acid green ~5, Naphthol green B, red dyes such as chromotrope 2B, Direct red 81, and ~lue dyes such as a~id blue 80, Chicago sky blue, and ani}ine blu~.
A variety of the above acid dyes can be modified in accordance with the practice of the invention for use in polyamic acids. The sodium cations which are charac~eristic of the acid dyes can be replaced with a variety of onium cations, typically quaternary ammonium or phosphonium cations such as benzyltrimethylammonium, tetrabutylammonium, tetraethylammonium, and tetrabutylphosphonium. The modified dyes can be prepared hy extraction of an agueous slurry of the commercial acid dye with methylene chloride. The solvent can be stripped to obtain the modified dye in high yield. The modified dyes were found to be soluble in N-methylpyrrolidone, in polyamic acid films and in polyimide films. The visible spectra of the onium salt dyes were undistinguishable from the sodium cation dyes.
The silicone polyamic acid used in the practice of the present invention is preferably prepared by a two-step process from aryldiamine and mixtures of norbornane 132~3~ RD-17,379 anhydride terminated organosiloxane, hereinafter referred to as "DiSiAn" and organic aromatic dianhydride which is preferably benzophenone dianhydride or hereinafter "BTDA".
An intercondensation solution can be used having from 10% to 30% by weight solids in a dipolar aprotic solvent. Among the dipolar aprotic solvents which can be used in the practice of the method of the present invention to prepare the silicone polyamic acid, there are included N-methylpyrrolidone, N,N-dimethylformamide.
Preferably, N-methylpyrrolidone is used as the dipolar aprotic solvent. Preferably a two-step process can be used where the ratio of DiSiAn to BTDA can be varied.
The preferred procedure is to ensure incorporation of the less reactive DiSiAn with aryldiamine for 30-60 minutes at about 90 to 100C. Incorporation of the BTDA can then proceed. During intercondensation, the mixture can be agitated, such as by stirring. After dissolution of the BTDA, the solutio~ can be maintained at 100 to 110C for an additional hour.
If desired, from 2% to 30% by weight of a suitable organic dye which is compatible with the silicone polyamic acid can be added with stirring. The tinted polyamic acid can then be spread as a thin film at thicknesses of from 1 to 20 microns on a suitable transparent substrate such as glass, silicon substrate or thermoplastic, for example polymethylmethacrylate, 'ILexan''* polycarbonate, thereafter hea ed to a temperature in the range ~f from 100C to 125C
to effect the removal of excess organic solvent. When the dried polyamic acid film is substantially tack~free, a suitable positive photoresist or negative photoresist can be spin coated onto its surface. The photoresist can be applied to a thickness of about .5 to 2 microns. The resulting composite can then be heated at a temperature from *Trademark 1 32030~ RD-17,379 80C to 100C to effect the removal of excess solvent, such as water or inert organic solvent.
In a preferred procedure for maki~q the silicone polyamic acid, an excess of the aryldiamine is avoided to minimize the production of gelled particles which can adv~rsely alter the film characteristics of the resulting silicone polyamic acid and silicone polyimide.
A color filter can be prepared in accordance with the practice of the method of the present invention on a transparent substrate utilizing a step-wise procedure for applyin~ tinted silicone polyimide. For example, a transparent substrate can be initially patterned with transparent silicone polyamic acid, tinted red, in accordance with the aforedescribed procedure. The silicone polyamic acid can thereafter be imidized by heating to a temperature of 200C for 60 minutes. The red tinted silicone polyimide will transmit red light, which can be patterned on the transparent substrate as an array of sguares, 250 microns on each side. Areas free of tinted silicone polyimide will transmit white light. The sub~trate can then be treated with additional tinted silicone polyamic acid, for example blue tinted silicone polyamic acid, and the process repeated. By the proper choice of masks and tinted silicone polyamic acid, a color filt~r can be made Z5 capable of exclusively transmitting blue, green and red light.
The following examples are given by way of illustration an~ not by way of limitation. All parts are by weight.
A mixture of 3.7008 grams (8.00 millimoles) of 5,5'-(1,1,3,3 tetramethyl-1,1,3-disiloxanediyl)-bis-norbor-9 _ ~32Q3~ RD-17,379 nane-2,3-dicarboxylic anhydride (DiSiAn), 2.1412 grams (19.8 millimoles) of metaphenylenediamine (MPD), and 23 grams of N~methylpyrrolidone (NMP) was warmed with stirring to 60C
for 30 minutes to effect complete solution and the formation of a silicone polyamic acid. There was then added to the mixture 3.9326 grams (12.20 millimoles) of benzophenonedianhydride (BTDA), while the mixture was stirred to provide a molar proportion of 40:60 of DiSiAn to BTDA units in the mixture. The mixture was then heated with stirring to 80C and aliquots were withdrawn at 10-minute intervals. Approximately 5 mil thick films were drawn onto glass slides and dried at 100C for 30 minutes. Some of the film were baked an additional 30 minutes at 200C. The solubilities of the resulting films were then tested by immersing them in a 0.5% by weight of aqueous tetramethyl ammonium hydroxide or sodium hydroxide solution "aqueous caustic" and also by baking the films an additional 30 minutes at 200C followed by immersion in NMP to determine their solubility in NMP. The following results show the aqueous caustic and NMP solubilities of films obtained from aliquots of silicone polyamic acid withdrawn at 10-minute intervals over a period of from 0 to 120 minutes from the reaction mixture.
~32~30~ RD-17,379 Time (min) 0.5% Agu~ous Caustic NMP
.
O s ~ i s ~0 s s s s 120 i3 1 - Samples dried 30 min @ 100C, 30 sec immersion 2 - Samples dried 30 min @ lDOQC followed.by 30 min @
200C, 1 min immersion in NMP followed by a water wash 3 - Soluble after 60 sec 4 - Time at 80C in reaction vessel The above results show that the silicone polyamic acid made in accordance with the practice of the present invention can be photopatterned using a standard agueous caustic positive resist developer, and resist the effects of a subsequent treatment with organic solvent used to remove the developed photoresist.
Silicone polyamic acid made in accordance with the practice of the invention was further evaluated for ability to resist imidization after being heated at 120C beyond a 30-minute drying period ~s shown in Table 1. The following results were obtained:
132~3~0 RD-17,379 Drying Time (100C~ (min) 0.5% Aqueous Causticl NMP~
0 5 s s s 4~ s s 9~ s 1~0 s 1 - 30 sec Immersion in 0.27 N aqueous Bu4NOH
2 - After baking at 200C for 30 min, 1 min immersion The above results show that the silicone polyamic acid made in accordance with the practice of the present invention can be dried at 100C for an extended period of time without significantly affecting its ability to be patterned in a~ueous caustic during the development of the photopatterned positive photoresist, while resisting subsequent treatment during the removal of the resist residue with an organic solvent prior to imidization.
In accordance with the procedure of Example 1, silicone polyamic acid ~ilms were prepared which were blended wi$h 30% by weight of "Sudan Black B'l**. "Pyralin"*
polyimide, a commercial polyamic acid manufactured by E.I.
duPont de Nemours & Co. of Wilmin~ton, Delaware, was also blended with 30% by weight of "Sudan Black B"**. Polyamic acid films were prepared from the blends and dried at 100C for 30 minutes and then developed as shown in the following *Trademark **Trademark . -12-132~3~ RD-17,379 table, where silicone copolymer is the silicon polyamic acid made in accordance with Example 1:
Silicone . Develop Timel Copol~mer Pyralin Polyimide .
30 sec s i - swells 90 sec s partial lift 120 sec s break-up insoluble l - Immersed in 0.27 N Bu4NOH
The above results show that after a 30-minute drying period at 120C, the commercially available Pyralin polyimide was insoluble in the aqueous caustic. After 120 seconds of immersion time in the aqueou-C caustic the Pyralin polyamic acid remained totally insoluble but, in addition, began to break up~
Additional silicone polyamic acids were prepared in accordance with the procedure shown in Example 1, except that in one instance Bisphenol-A dianhydride was used in place of the DiSiAn to produce a silicone polyamic acid having approximately the same proportions of BPADA units and BTDA in the silicone polyamic acid. It was found that the silicone polyamic acid free of the DiSiAn units was insoluble when immersed in the aqueous caustic after a 30-minute drying period at 100C.
~ 3 2 ~ 3 ~ ~ R~-17,379 In accordance with the procedure o Example 1, there was stirred a mixture to 80C for 1.5 hours consisting of 39.3483 grams (0.19651 mole) of oxydianiline, 22.7259 grams (0.04913 mole) of DiSiAn, and 250 ml of NMP. After 1.5 hours, ~here was then added to the mixturls 47.4900 grams (0.14738 mole) of benzophenone dianhydride along with 160 ml of NMP. The mixture was warmed to 110C upon mixing and was allowed to cool to 100C. The mixture was stirred and maintained at lOO~C for 2 hours and then cooled to room temperature.
There was added to a portion of the above silicone polyamic acid, a sufficient amount of the bis(tetrabutylammonium) salts of acid green #41 dye to provide a mixture having about 20% by weight of the dye based on the total weight of dye and silicone polyamic acid.
The dye was prepared by the ollowing procedure. A mixture was stirred at room temperature for one hour consisting of 8.7 grams (5.31 millimoles) of acid green #41 (dye content 40%), 2.9S grams (10.6 millimoles) of tetrabutylammonium chloride, 150 ml of water, and 150 ml of methylene chloride.
The mixture was stirred at room temperature for one hour and at last separated. The solvent was removed rom the organic layer under reduced pressure and the resulting solid dried in vacuo at 80C to obtain 5.1 grams (88%) of an intense green dye as a bis(tetrabutylammonium) salt.
A solution of the above silicone polyamic acid and green dye in sufficient N-methyl pyrrolidone to produce a 20% by weight mixture was spin coated onto a silicone wafer using a headway photoresist spinner model EClOl operating at 3500 rpm for 20 seconds. After baking the applied silicone polyamic acid for 30 minutes at 110C, the resulting surface of the polyamic acid was found to be tack free. Photoresist (KTI 809) was then spun onto the treated silicone wafer and ~ ~ 2 ~ RD-17,379 dried at 90C for 30 minutes to pr~duce a one micron layer of photoresist on about a 4.5 micron silicone polyamic acid film. The wafer was then patterned using an "Oriel"* exposure station with a 30-second exposure. "Shipley Mi.croposit 312"*
developer diluted l:l with distilled water was then employed to develop the photoresist and polyamic acid by immersing the treated wafer in the developing solution for 1 minute at 25C.
The patterned combination of resist and silicone polyamic acid was washed free of the developing solution ancl then further dried at ~40~C for 30 minutes. The photoresist was then stripped off with butylacetate solvent and the wafer dried.
The above photopatterned polyamic acid treated silicone wafer now free of resist was then heated to 200C
for 60 minutes to fully imidize the silicone polyamic acid.
The above procedure was repe~ted with silicone polyamic acid tinted with blue and red dye to provide for the-production of a color filter consisting of a 3-10 micron ?0 thick silicone polyamic acid converted to a silicone-polyimide and patterned in 250 micron by 250 micron sguares of blue, green, and red.
Although the above examples are directed to only a few of the very many variables which can be used in the practice of the method of ~he present invention and to the products obtained therefrom, it should be understood that the method and products of the present invention are more broadly defined in the description preceeding these examples.
*Trademark ~15-
.
O s ~ i s ~0 s s s s 120 i3 1 - Samples dried 30 min @ 100C, 30 sec immersion 2 - Samples dried 30 min @ lDOQC followed.by 30 min @
200C, 1 min immersion in NMP followed by a water wash 3 - Soluble after 60 sec 4 - Time at 80C in reaction vessel The above results show that the silicone polyamic acid made in accordance with the practice of the present invention can be photopatterned using a standard agueous caustic positive resist developer, and resist the effects of a subsequent treatment with organic solvent used to remove the developed photoresist.
Silicone polyamic acid made in accordance with the practice of the invention was further evaluated for ability to resist imidization after being heated at 120C beyond a 30-minute drying period ~s shown in Table 1. The following results were obtained:
132~3~0 RD-17,379 Drying Time (100C~ (min) 0.5% Aqueous Causticl NMP~
0 5 s s s 4~ s s 9~ s 1~0 s 1 - 30 sec Immersion in 0.27 N aqueous Bu4NOH
2 - After baking at 200C for 30 min, 1 min immersion The above results show that the silicone polyamic acid made in accordance with the practice of the present invention can be dried at 100C for an extended period of time without significantly affecting its ability to be patterned in a~ueous caustic during the development of the photopatterned positive photoresist, while resisting subsequent treatment during the removal of the resist residue with an organic solvent prior to imidization.
In accordance with the procedure of Example 1, silicone polyamic acid ~ilms were prepared which were blended wi$h 30% by weight of "Sudan Black B'l**. "Pyralin"*
polyimide, a commercial polyamic acid manufactured by E.I.
duPont de Nemours & Co. of Wilmin~ton, Delaware, was also blended with 30% by weight of "Sudan Black B"**. Polyamic acid films were prepared from the blends and dried at 100C for 30 minutes and then developed as shown in the following *Trademark **Trademark . -12-132~3~ RD-17,379 table, where silicone copolymer is the silicon polyamic acid made in accordance with Example 1:
Silicone . Develop Timel Copol~mer Pyralin Polyimide .
30 sec s i - swells 90 sec s partial lift 120 sec s break-up insoluble l - Immersed in 0.27 N Bu4NOH
The above results show that after a 30-minute drying period at 120C, the commercially available Pyralin polyimide was insoluble in the aqueous caustic. After 120 seconds of immersion time in the aqueou-C caustic the Pyralin polyamic acid remained totally insoluble but, in addition, began to break up~
Additional silicone polyamic acids were prepared in accordance with the procedure shown in Example 1, except that in one instance Bisphenol-A dianhydride was used in place of the DiSiAn to produce a silicone polyamic acid having approximately the same proportions of BPADA units and BTDA in the silicone polyamic acid. It was found that the silicone polyamic acid free of the DiSiAn units was insoluble when immersed in the aqueous caustic after a 30-minute drying period at 100C.
~ 3 2 ~ 3 ~ ~ R~-17,379 In accordance with the procedure o Example 1, there was stirred a mixture to 80C for 1.5 hours consisting of 39.3483 grams (0.19651 mole) of oxydianiline, 22.7259 grams (0.04913 mole) of DiSiAn, and 250 ml of NMP. After 1.5 hours, ~here was then added to the mixturls 47.4900 grams (0.14738 mole) of benzophenone dianhydride along with 160 ml of NMP. The mixture was warmed to 110C upon mixing and was allowed to cool to 100C. The mixture was stirred and maintained at lOO~C for 2 hours and then cooled to room temperature.
There was added to a portion of the above silicone polyamic acid, a sufficient amount of the bis(tetrabutylammonium) salts of acid green #41 dye to provide a mixture having about 20% by weight of the dye based on the total weight of dye and silicone polyamic acid.
The dye was prepared by the ollowing procedure. A mixture was stirred at room temperature for one hour consisting of 8.7 grams (5.31 millimoles) of acid green #41 (dye content 40%), 2.9S grams (10.6 millimoles) of tetrabutylammonium chloride, 150 ml of water, and 150 ml of methylene chloride.
The mixture was stirred at room temperature for one hour and at last separated. The solvent was removed rom the organic layer under reduced pressure and the resulting solid dried in vacuo at 80C to obtain 5.1 grams (88%) of an intense green dye as a bis(tetrabutylammonium) salt.
A solution of the above silicone polyamic acid and green dye in sufficient N-methyl pyrrolidone to produce a 20% by weight mixture was spin coated onto a silicone wafer using a headway photoresist spinner model EClOl operating at 3500 rpm for 20 seconds. After baking the applied silicone polyamic acid for 30 minutes at 110C, the resulting surface of the polyamic acid was found to be tack free. Photoresist (KTI 809) was then spun onto the treated silicone wafer and ~ ~ 2 ~ RD-17,379 dried at 90C for 30 minutes to pr~duce a one micron layer of photoresist on about a 4.5 micron silicone polyamic acid film. The wafer was then patterned using an "Oriel"* exposure station with a 30-second exposure. "Shipley Mi.croposit 312"*
developer diluted l:l with distilled water was then employed to develop the photoresist and polyamic acid by immersing the treated wafer in the developing solution for 1 minute at 25C.
The patterned combination of resist and silicone polyamic acid was washed free of the developing solution ancl then further dried at ~40~C for 30 minutes. The photoresist was then stripped off with butylacetate solvent and the wafer dried.
The above photopatterned polyamic acid treated silicone wafer now free of resist was then heated to 200C
for 60 minutes to fully imidize the silicone polyamic acid.
The above procedure was repe~ted with silicone polyamic acid tinted with blue and red dye to provide for the-production of a color filter consisting of a 3-10 micron ?0 thick silicone polyamic acid converted to a silicone-polyimide and patterned in 250 micron by 250 micron sguares of blue, green, and red.
Although the above examples are directed to only a few of the very many variables which can be used in the practice of the method of ~he present invention and to the products obtained therefrom, it should be understood that the method and products of the present invention are more broadly defined in the description preceeding these examples.
*Trademark ~15-
Claims (17)
1. A method for patterning adherent silicone polyamic acid on the surface of at least a portion of a substrate, where the silicone polyamic acid is patterned by (1) spin coating a silicone polyamic acid onto the surface of the substrate, (2) drying the silicone polyamic acid at a temperature of at least 100°C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned UV light, and (5) developing the resulting patterned silicone polyamic acid-photoresist composite, where the silicone polyamic acid is the intercondensation product of reaction of about 2% less than stoichiometric, to about stoichiometric, of aryldiamine and organic dianhydride, comprising a mixture of from 20 to 80 mole percent of norbornane anhydride terminated organosiloxane and from 80 mole percent to 20 mole percent of aromatic organic bisanhydride.
2. The method of claim 1 in which the patterned silicone polyamic acid is imidized to form a patterned silicone polyimide, which method includes the further steps of (6) stripping the remaining photoresist from the surface of the silicone polyamic acid with an organic solvent, and (7) heating the silicone polyamic acid until fully imidized, where the silicone polyamic acid is the product of reaction of substantially equal molar amounts of aryldiamine and organic dianhydride comprising a mixture of norbornane anhydride terminated organosiloxane and aromatic organic bisanhydride.
3. The method of claim 2 where the substrate is transparent.
4. The method of claim 2, where the silicone polyimide is tinted with a dye.
5. The method of claim 4, where the dye is a blue, green or red dye, or a combination thereof.
6. The method of claim 4, where the polyamic acid composition comprises up to 40% by weight of a compatible onium salt organic dye.
7. The method of claim 6, where the onium salt is a bis(tetrabutylammonium) salt.
8. The method of claim 4, where the silicone polyamic acid composition comprises up to 40% by weight of a compatible organic dye which is stable up to a temperature of 125°C.
9. The method of claim 6, where the organic dye is a blue dye.
10. The method of claim 6, where the organic dye is a red dye.
11. The method of claim 6, where the organic dye is a yellow dye.
12. The method of claim 6, where the organic dye has a maximum absorption between 200 nm to 450 nm.
13. A method which comprises:
(1) spin coating onto a substrate a silicone polyamic acid having an effective amount of an organic dye with maximum absorption in the range of 200 to 450nm, (2) drying the silicone polyamic acid at a temperature of at least 100°C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite, (6) etching exposed substrate through the patterned silicone polyamic acid-photoresist composite, and (7) stripping the silicone polyamic acid-photoresist composite from the resulting etched substrate, where the silicone-polyamic acid is as previously defined in claim 1.
(1) spin coating onto a substrate a silicone polyamic acid having an effective amount of an organic dye with maximum absorption in the range of 200 to 450nm, (2) drying the silicone polyamic acid at a temperature of at least 100°C, (3) spin coating a positive photoresist onto the surface of the silicone polyamic acid to produce a silicone polyamic acid-photoresist composite, (4) exposing the applied positive photoresist to patterned UV light, (5) developing the resulting patterned silicone polyamic acid-photoresist composite, (6) etching exposed substrate through the patterned silicone polyamic acid-photoresist composite, and (7) stripping the silicone polyamic acid-photoresist composite from the resulting etched substrate, where the silicone-polyamic acid is as previously defined in claim 1.
14. A method in accordance with claim 11, where the organic dye is coumarin.
15. A method in accordance with claim 1, wherein the surface of the substrate is reflective.
16. A method in accordance with claim 1, where the substrate is aluminum.
17. A method in accordance with claim 1, wherein the organic dianhydride comprises a mixture of from about 30 to 70 mole percent of norbornane anhydride terminated organosiloxane and from about 70 mole percent to 30 mole percent of aromatic organic bisanhydride.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/033,938 US4782009A (en) | 1987-04-03 | 1987-04-03 | Method of coating and imaging photopatternable silicone polyamic acid |
GB8806011A GB2204316B (en) | 1987-04-03 | 1988-03-14 | Photopatternable silicone polyamic acid, method of making and use |
DE3809143A DE3809143A1 (en) | 1987-04-03 | 1988-03-18 | MEDICINE PATTERNABLE SILICONE POLYAMID ACID, METHOD FOR THE PRODUCTION AND USE THEREOF |
FR888804324A FR2613499B1 (en) | 1987-04-03 | 1988-03-31 | SILICONE-POLYAMIC ACID OF WHICH A PHOTOGRAPHIC DRAWING CAN BE FORMED, PROCESS FOR COATING A SUBSTRATE THEREOF AND SUBSTRATE COATED WITH SUCH AN ACID |
JP63081471A JPS64950A (en) | 1987-04-03 | 1988-04-04 | Silicon polyamic acid which enables optical pattern transfer, its production and its use method |
CA000565353A CA1320300C (en) | 1987-04-03 | 1988-04-28 | Photopatternable silicone polyamic acid, method of making and use |
US07/229,667 US4855199A (en) | 1987-04-03 | 1988-08-08 | Photopatterned product of silicone polyamic acid on a transparent substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/033,938 US4782009A (en) | 1987-04-03 | 1987-04-03 | Method of coating and imaging photopatternable silicone polyamic acid |
CA000565353A CA1320300C (en) | 1987-04-03 | 1988-04-28 | Photopatternable silicone polyamic acid, method of making and use |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1320300C true CA1320300C (en) | 1993-07-13 |
Family
ID=25671869
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000565353A Expired - Fee Related CA1320300C (en) | 1987-04-03 | 1988-04-28 | Photopatternable silicone polyamic acid, method of making and use |
Country Status (6)
Country | Link |
---|---|
US (1) | US4782009A (en) |
JP (1) | JPS64950A (en) |
CA (1) | CA1320300C (en) |
DE (1) | DE3809143A1 (en) |
FR (1) | FR2613499B1 (en) |
GB (1) | GB2204316B (en) |
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US4855199A (en) * | 1987-04-03 | 1989-08-08 | General Electric Company | Photopatterned product of silicone polyamic acid on a transparent substrate |
GB8917191D0 (en) * | 1989-07-27 | 1989-09-13 | Gec Avery Technology | Strain gauge encapsulation process |
JP2551214B2 (en) * | 1990-08-06 | 1996-11-06 | 信越化学工業株式会社 | Curable resin solution composition, method for producing the same, and protective film for electronic parts |
US5114757A (en) * | 1990-10-26 | 1992-05-19 | Linde Harold G | Enhancement of polyimide adhesion on reactive metals |
JPH04351667A (en) * | 1991-05-29 | 1992-12-07 | Shin Etsu Chem Co Ltd | Curable resin composition and protective film for electronic component |
US5177181A (en) * | 1991-06-06 | 1993-01-05 | Occidental Chemical Corporation | Diamines and photosensitive polyimides made therefrom |
DE4203781C1 (en) * | 1992-02-10 | 1993-09-09 | Du Pont De Nemours (Deutschland) Gmbh, 61352 Bad Homburg, De | |
JP2694097B2 (en) * | 1992-03-03 | 1997-12-24 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Antireflection coating composition |
US5397684A (en) * | 1993-04-27 | 1995-03-14 | International Business Machines Corporation | Antireflective polyimide dielectric for photolithography |
EP0949277A3 (en) * | 1995-06-22 | 2000-12-27 | Yuri Gudimenko | Surface modification of polymers and carbon-based materials |
US5980768A (en) * | 1997-03-07 | 1999-11-09 | Lam Research Corp. | Methods and apparatus for removing photoresist mask defects in a plasma reactor |
US5998569A (en) * | 1998-03-17 | 1999-12-07 | International Business Machines Corporation | Environmentally stable optical filter materials |
US6048662A (en) * | 1998-12-15 | 2000-04-11 | Bruhnke; John D. | Antireflective coatings comprising poly(oxyalkylene) colorants |
WO2000077575A1 (en) | 1999-06-10 | 2000-12-21 | Alliedsignal Inc. | Spin-on-glass anti-reflective coatings for photolithography |
US6824879B2 (en) | 1999-06-10 | 2004-11-30 | Honeywell International Inc. | Spin-on-glass anti-reflective coatings for photolithography |
DE10103524A1 (en) * | 2001-01-26 | 2002-08-22 | Infineon Technologies Ag | Method and semiconductor arrangement for etching a layer of a semiconductor substrate by means of a silicon-containing etching mask |
US6765276B2 (en) * | 2001-08-23 | 2004-07-20 | Agilent Technologies, Inc. | Bottom antireflection coating color filter process for fabricating solid state image sensors |
US8344088B2 (en) | 2001-11-15 | 2013-01-01 | Honeywell International Inc. | Spin-on anti-reflective coatings for photolithography |
US8053159B2 (en) | 2003-11-18 | 2011-11-08 | Honeywell International Inc. | Antireflective coatings for via fill and photolithography applications and methods of preparation thereof |
JP4563076B2 (en) * | 2004-05-26 | 2010-10-13 | 東京応化工業株式会社 | Antireflection film forming composition, antireflection film comprising antireflection film forming composition, and resist pattern forming method using the antireflection film forming composition |
JP4541944B2 (en) * | 2005-03-25 | 2010-09-08 | 株式会社きもと | Photosensitive polyimide resin composition |
JP4573039B2 (en) * | 2005-06-14 | 2010-11-04 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
US8557877B2 (en) | 2009-06-10 | 2013-10-15 | Honeywell International Inc. | Anti-reflective coatings for optically transparent substrates |
US8864898B2 (en) | 2011-05-31 | 2014-10-21 | Honeywell International Inc. | Coating formulations for optical elements |
KR101354640B1 (en) | 2011-12-30 | 2014-01-27 | 제일모직주식회사 | Positive type photosensitive resin composition |
JP6803842B2 (en) | 2015-04-13 | 2020-12-23 | ハネウェル・インターナショナル・インコーポレーテッドHoneywell International Inc. | Polysiloxane formulations and coatings for optoelectronic applications |
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US4696890A (en) * | 1985-04-11 | 1987-09-29 | Ciba-Geigy Corporation | Processes for preparing protective coatings and relief structures |
JPS6247045A (en) * | 1985-08-20 | 1987-02-28 | インタ−ナショナル ビジネス マシ−ンズ コ−ポレ−ション | Polyimide composition and formation of film having pattern |
-
1987
- 1987-04-03 US US07/033,938 patent/US4782009A/en not_active Expired - Fee Related
-
1988
- 1988-03-14 GB GB8806011A patent/GB2204316B/en not_active Expired - Fee Related
- 1988-03-18 DE DE3809143A patent/DE3809143A1/en not_active Ceased
- 1988-03-31 FR FR888804324A patent/FR2613499B1/en not_active Expired - Lifetime
- 1988-04-04 JP JP63081471A patent/JPS64950A/en active Pending
- 1988-04-28 CA CA000565353A patent/CA1320300C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
GB8806011D0 (en) | 1988-04-13 |
GB2204316B (en) | 1991-10-23 |
FR2613499A1 (en) | 1988-10-07 |
GB2204316A (en) | 1988-11-09 |
JPS64950A (en) | 1989-01-05 |
FR2613499B1 (en) | 1990-08-03 |
DE3809143A1 (en) | 1988-10-13 |
US4782009A (en) | 1988-11-01 |
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