TW556045B - Photosensitive polyimide precursor compositions - Google Patents

Abstract

Reducing inhibition of the photochemical crosslinking by including in the photosensitive polyimide precursor composition a metal inhibitor selected from 1H-tetrazole, 1,2-cyclohexenediamine tetraacetic acid hydrate and 5-mercaptobenzimidazole.

Description

V. Description of the invention (4) (νιι) A photosensitizer compound (1) of 0.1 to 2.0 parts by weight. 〇111) 0.05-2.0 parts by weight of the adhesion-promoting compound ()). Polyurethane polymer (C) has a number average polymerization degree of 5 to 1,000, and is synthesized by the following (1) polycondensation reaction of monomer A & B ...

Monomer A is obtained by the reaction of a dianhydride compound with an alcohol r, 0h to produce a diester_dioic acid, which is then converted into a diester-dioic acid chloride by an appropriate reagent ( Chemical formula 2).

(Chemical Formula 2) R group represents a tetravalent aromatic group containing at least one 6-membered carbocyclic ring, in which a tetracarbonyl group is directly connected to a different carbon atom of R, and each of two to four groups is connected to Adjacent carbon atoms. The dianhydride compound may be selected from one or more of the following dianhydrides: pyromellitic dianhydride (pMDA), 3,3 ,, 4,4, benzophenone tetracarboxylic dianhydride (BTDA), 3, 3,4,4, -bisphenyltetrajunic acid di 556045 5. Description of the invention (5) (BPDA), 3,3,4,4, -diphenylphosphonium tetracarboxylic dianhydride, 4,4 __ Perfluoroisopropylidene diphthalic dianhydride (6FDa), 4,4, -oxydiphthalic anhydride (ODPA), bis (3,4 · dicarboxy) tetramethyldisiladian dianhydride, bis (3,4-dicarboxyphenyl) dimethyl sulfanedioic dianhydride, cyclobutane tetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. The tetracarboxylic dianhydride can be used alone or in combination, and the choice of the dianhydride compound is not limited to the compounds shown above. The R 'group contains at least one unsaturated group, which may be vinyl, dipropyl, propenyl, methacryl, alkynyl, cyano, or other suitable radiation-crosslinkable groups. The monomer B is a divalent diamine, wherein the R1 group contains at least one 6-membered carbocyclic ring and is selected from at least one of the following groups: divalent aromatic, heterocyclic, alicyclic or aliphatic amine: m- Phenylenediamine, p-phenylenediamine, 2,2, _bis (trifluoromethyl) -4,4, -diamino-1, 丨, _biphenyl, 3,4, diaminodiphenyl Ether, 4,4, monoaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4-toluenediamine, 3,3'-diaminodiphenylphosphonium, 3, 4, -diaminodiphenylphosphonium, 4,4, -diaminodiphenylphosphonium, 3,3, -diaminodiphenylmethane, 4,4, -diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4, -diaminodiphenylmethane, 4,4, -diaminodiphenylketone, 3,3, diaminodiphenylketone , 3,4, _ diaminodiphenyl ketone, 1,3-bis (4-aminophenoxy) benzene, i, 3 • bis (3-amino-phenoxy) benzene, 1,4 -Bis (7-aminopropyl) tetramethyldisilazane, 253,5,6-tetrafluorenyl-p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, arsine Amine, Tetramethylenediamine, Pentamethylenediamine, Hexamethylenediamine, 2,5-Amidino Methylenediamine, 3-methoxyhexamethylenediamine, heptamethyldiamine, 2,5-dimethylheptyldiamine, 3-methylheptamyldiamine, 4,4-Dimethyl heptenyl diamine, octadecyl diamine, nonafluorenyl group 556045 5. Description of the invention (6) diamine, 2,5-dimethyl nonadecyl diamine, Decyldiamine, ethylenediamine, propylenediamine, 2,2-dimethylpropanediamine, 1,10-diamino-fluorene, ιo-dimethyldecane, 2,110 diamine Dodecane, 1,12-diaminooctadecane, 2,17-diamino eicosane, 3,3, -dimethyl-4,4, -diaminodiphenylmethane, bis (4 · aminocyclohexyl) methane, 3,3, -diaminodiphenylethane, 4,4'-diaminodiphenylethene, and 4,4, diaminodiphenylsulfide Compounds, 2,6-diamino group 0 ratio σ, 2,5-diaminopyridine, 2,6-diamino-4-trifluoromethylpyridine, 2,5-diamino group 1, 3 , 'Oxadiazole, 1,4 · diaminocyclohexane, piperazine, 4,4, -fluorenyldiphenylamine, 4,4'-methylidene · bis (o-chloroaniline), 4, 4'-methylidene-bis (3-methylaniline), 4,4, -methylidene-bis (2-ethylaniline), 4,4,- Methylene-bis- (2-methoxyaniline), 4,4, -oxy-diphenylamine, 4,4, -oxy-bis (2-methoxybenzylamine), 4,4'-oxy · Bis (2-Gasaniline), 4,4, -thio-diphenylamine, 4,4, -thio-bis- (2-methylaniline), 4,4, -thio-bis- (2- Methoxyaniline), 4,4,-sulfo-bis- (2-gasaniline), 3,3, -sulfo-diphenylamine, 3.3, _sulfo_diphenylamine. The choice of monomer B is limited to these compounds, and monomer β can be used alone or in combination. Photoinitiator D is at least one selected from the group consisting of: Chemical formula 3 Chemical formula 4

556045

V. Description of the invention (7) That is, bis (77.5_2,4_cyclopentadiene _;! _ Group) _bis (2,6_ difluoro_3_ (ih_suple-i-yl) phenyl) titanium), and Bis (fluorenylcyclopentadienyl) _bis (26_difluoroben-1-yl) zin. The photocrosslinking agent (E) is selected from at least one selected from the group consisting of acrylic acid or methacrylic acid and aromatic and especially aliphatic polyhydric alcohols having 2-3 (H @ c atom or 5 or Esters and partial esters of cycloaliphatic polyols with 6 C carbon atoms. Examples of suitable components (E) are: · propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate Ester, diethylene glycol difluorenyl acrylate, trimethylene glycol diacrylate, trimethylene glycol difluorenyl acrylate, tetraethylene glycol diacrylate, tetraethylene glycol monomethyl acrylate S Purpose, polyethylene glycol di (meth) acrylates with an average molecular weight in the range of 200-2 000, difluorenyl alcohol propylene glycol ethanol vinegar tris (fluorenyl) with an average molecular weight in the range of 500-1500 Acrylic acid, pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. The metal inhibitor compound (F) is selected from the group consisting of the following At least one of the groups: 1H-tetrazole, 1,2-cyclohexanediamine tetraacetic acid hydrate The polymerization inhibitor (G) is selected from the group consisting of p-benzoquinone, thiodiphenylamine, and alkyl alcohols such as 4-tert-butylphenol, 2, 5-di-tertiary-butylhydroquinone or 2,6-di-tertiary-butyl-4-fluorenyl phenol). The solvent (ii) is selected from 2-methylpyrrolidone, 7-butane Esters, Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, dimethyl sulfoxide, cyclobutane, ethylene glycol monomethyl ether, cyclopentanone, propylene glycol monomethyl Ether Acetate 10 556045 V. Description of the Invention (10) Example 1 A negative photoresist composition prepared by mixing the following: 37.03% by weight polyamidate (component C), which is derived from Preparation of 4,4, -oxydiphthalic anhydride (= ODPA), 4,4, -diaminophenyl ether (= 〇da), and 2-wt% ethyl methyl acrylate (R ') Corresponds to titanium octadecane of chemical formula 3 (component D) 5. 36% by weight of tetraethylene glycol dimethacrylate (component E) ^ 5% by weight Η tetrazolium (component F) 〇 .07 wt% ^ -benzoquinone (component G) wt% silane adhesion promoter (component J) 2.25 wt% % Ν-methylpyrrolidone (component Η)

This composition was rolled overnight to produce a clear resin solution, and then filtered under pressure through a 0.2 micron hole width filter. The resin solution was spin-coated on the bare silicon wafer and the coated silicon wafer, and then at 100. The hot plate was dried for 7 minutes. In this way, a film with a uniform thickness of 11 # m was obtained on the wafer. Then, the wafer was exposed to monochromatic light having a wavelength of 365 nm using a Canon 300i i-line stepper exposure tool. After exposure, the image was rotated by rotating the wafer at 1000 rpm and then spraying the wafer with cyclopentanone for 35 seconds. Thereafter, the same volume of cyclopentanone and propylene glycol monomethyl ether acetate (PGMEA) were applied simultaneously at 1000 The wafer was sprayed at rpm for 10 seconds, and then sprayed with pure PGMEA for 15 seconds to develop. In the final step, the wafer is rotated to dryness at 3000 rpm. High-quality convex images were obtained on silicon wafers and copper-coated silicon wafers. The exposure dose required to obtain 90% of the retained film thickness after development on the two substrates was 300 mJ / cm2. 13 556045

V. Description of the invention (u) Example 2 A negative photoresist composition prepared by mixing the following: 37.34% by weight of polyamino acid S (component C), which is derived from 4,4'-oxydi Preparation of uric anhydride (= ODPA), 4,4, -diaminophenyl ether (= 〇DA) and 2-hydroxyethyl methacrylate (R,) 6.54% by weight, corresponding to titanium dicenelocene of chemical formula 4 20% NMP solution (component D) 5.61% by weight tetraethylene glycol difluorenyl acrylate (component E) 0.0 5% by weight 1H-tetrazole (component F) J 3.07% by weight 177¾ quinone ( Component G) '" ^ 〇.74% by weight silane adhesion promoter (component J) 49.64% by weight N-methylpyrrolidone (component η) This composition was rolled overnight to produce a clear resin solution, and then passed through 0.2 U-meter pore width pressure filter. The resin solution was spin-coated on bare silicon wafers and copper-coated silicon wafers, and then dried on a 10'rc hot plate for 7 minutes. In this way, 11 # m thick uniform film thickness Obtained on the wafer. Then, the wafer was exposed to monochromatic light with a wavelength of 365 nm using a Canon 300i i-line stepper exposure tool. After exposure, the image was rotated by the wafer at 1000 rpm And then spray the wafer with cyclopentanone for 35 seconds, and then simultaneously spray the wafer with equal volumes of cyclopentanone and propylene glycol monomethyl ether acetate (pGMEA) at 1000 rpm for 10 seconds, and then spray with pure pgmeA丨 Li 15 is developed and developed. In the final step, the wafer is rotated to dryness at 3000 rpm. The convex image of the high mouth is obtained on the silicon wafer and the silicon wafer coated with copper. 90% of the retained film is formed The thickness of the exposure dose is 120 mJ / cm2 for silicon wafers and 140 mJ / cm3 for copper wafers. 556045

Example 3 A negative photoresist composition is prepared by mixing the following: 26.44. *% ~~ acid ester (component C), which is a diphthalic anhydride (= ODPA), 4,4, · diamine group Phenyl ether (BODA) and 2-hydroxyethyl methacrylate (R,) were borrowed 0.93% by weight, corresponding to the titanocene (component D) of chemical formula 3 _ 3 · y 7 reset% tetraethyl #Basediol difluorenyl acrylate (component E) 0.034 reset% h2-cyclohexanediamine tetraacetic anhydride (component F) 0.053% by weight body-benzoquinone (component G) CDAC (group Part I) 0 · 5 3 Reset% Silane adhesion promoter (component J) 33.98% by weight (component H) — 33.98% by weight Ν-methylpyrrolidone (component η) This composition is rolled overnight to clarify The resin solution was then filtered under pressure. The resin solution was spin-coated on a silver-coated silicon wafer, and then dried on a hot plate at 100 ° C for 2 minutes. In this way, a film with a uniform thickness of 4.5 // m is obtained on the wafer. The wafer was then exposed to broadband exposure using an energy dose of 300 mJ / cm2 using a Karl Suss MA 56 contact exposure tool. After exposure, the image was rotated by rotating the wafer at 1000 rpm and then spraying the wafer with cyclopentanone for 10 seconds, and then simultaneously with equal volumes of cyclopentanone and propylene glycol monofluorenyl ether acetate (PGMEA). And the wafer was sprayed at 1000 rpm for 10 seconds, and then sprayed with pure PGMEA for 10 seconds to develop. In the final step, the wafer is rotated to dryness at 3000 rpm. High-quality convex images were obtained on silver-coated silicon wafers with 70% film thickness retention. 15 556045 5. Description of the invention (13) Example 4 A negative photoresist composition is prepared by mixing the following 38.28% by weight c), its anhydride (= PMDA), 4,4'_diamine group Phenyl scale (= 〇DA) and 2-hydroxyethyl methacrylate by 6.70 weight ° / 〇 correspond to 20% NMP solution (component D) of the titanocene of chemical formula 4 (component D) 5.74% reset 4 Ethylene glycol dimethyl acrylate (component 0.05 reset% 1H-tetrahydropyrene (component ρ) 0.08% by weight component g) " ~-0 · 7 6 weight. % Silane adhesion promoter (component J) 48.39% by weight N-methylpyrrolidone (component η) 'This composition is rolled overnight to produce a clear resin solution, and then pressurized through a 0.2 micron hole width filter filter. The resin solution was spin-coated on a bare silicon wafer and a copper-coated silicon wafer, and the wafer was dried on a 105 cc hot plate for 6 minutes. In this manner, a polymer layer having a uniform thickness of 15 to 17 / zm is obtained on the wafer. The wafer was then exposed to broadband radiation using a Kari Suss μα 56 contact exposure tool at an energy dose of 200 mJ / cm2. After exposure, the image was obtained by rotating the wafer at 1300 rpin and then spraying the wafer with QZ-3501 for 40 seconds. Thereafter, the same volume of 〇2_35〇1 and propylene glycol monomethyl ether acetate (pGMEA) were applied simultaneously and 300 rprn was sprayed on the wafer for 15 seconds, then developed with pure PGMEA and sprayed at 1300 rpm for 15 seconds. In the final step, the wafer is rotated to dryness at 3000 rpm. High-quality convex images are obtained on silicon wafers and copper-coated silicon wafers. 16 556045 5. Description of the invention (14) Example 5 A negative photoresist composition is prepared by mixing the following: 38.28 weight. / 〇 Polyamidate (component C), which is from pyromellitic dianhydride (= PMDA), 4,4, -diaminophenyl ether (= 〇DA) and 2-Ethyl ethyl Preparation of methacrylic acid vinegar (R) 34% by weight Corresponding to the titanocene (component D) of chemical formula 3 5.7 4% by weight tetraethylene glycol dimethacrylate (component E). 0.55% by weight 1H-tetrazole (component F) 0.08% by weight p-benzoquinone (component G) 0.776% by weight adhesion promoter (component J) 53.75% by weight N-methylpyrrolidone (component H) The composition is rolled overnight to produce a clear resin solution, and then filtered under pressure through a 0.2 micron hole width filter. The resin solution was spin-coated on a Cu-coated silicon wafer and then at 105. 〇 on a hot plate for 10 minutes. In this way, a polymer layer of uniform thickness of 30 to 35 // m is paid on the wafer. The 'wafer was then exposed to broadband spectral radiation using a Karl Suss MA 56 contact exposure tool at an energy dose of 500 mJ / cm2. After exposure, the image was rotated by rotating the wafer at 1300 rpm and then spraying the wafer at qZ_35〇1 for 80 seconds, and then at the same time with equal volumes of qZ_3501 and propylene glycol monomethyl isopropyl acetate (PGMEA) at 3000 rpm The wafer was sprayed for 15 seconds, and then developed with pure PGMEA and sprayed at 1300 rpm for 15 seconds. In the final step, the crystal circle was rotated at 3000 卬 m to dryness. High-quality convex images were obtained on copper-coated silicon wafers. An exposure energy of 500 mj / cm2 resulted in a film retention of 89.1% from the original soft baked film thickness development. 556045 V. Description of the Invention (15) Comparative Example 1 A negative photoresist composition prepared by mixing the following: 37.01% by weight of polyamidate (component C), which is derived from 4,4, -oxygen 1.3% by weight of diphthalic anhydride (= ODPA), 4,4, · diaminophenyl ether (= 〇da) and 2-hydroxyethyl methacrylate (R,) corresponding to chemical formula 3 Titanium (component D) 5.56% by weight tetraethylene glycol dimethacrylate (component 0.07% by weight p-benzoquinone (component G) 0.74% by weight silane adhesion promoter (component J) 55.32 % By weight of pyrrolidone (component H) This composition is rolled overnight to produce a clear resin solution, and then filtered under pressure through a filter with a hole width of 0.2 μm. The resin solution is spin-coated on bare stone wafers and coated with The copper-coated Shixi wafer was then dried on a hot plate at 105.0 for 8 minutes. In this way, a polymer layer with a uniform thickness of 20 # m was obtained on the wafer. Then, it was used Canon 300i line stepper exposure tool exposes the wafer to monochromatic light with a wavelength of 365 nm. After exposure, the image is exposed to 1000 r Rotate the wafer at pm and then spray the wafer with cyclopentanone for 70 seconds, and then simultaneously spray the wafer with equal volumes of cyclopentanone and n-butyl acetate (NBA) for 10 seconds at 1000 rPm , And then sprayed with pure NBA for 10 seconds to develop. In the final step, the wafer was rotated to dryness at 3000 rpm. A high-quality convex image was obtained on a silicon wafer, and the exposure energy at 410 mJ / cm2 was 91%. Film thickness retention. Copper wafers show very poorly defined patterns with poor adhesion, and a large number of films with 17% film thickness retention are lost.

18 556045 V. Description of the Invention (16) Comparative Example 2 A negative photoresist composition was prepared by mixing the following: 33.94% by weight of a polyamidate (component C), which is derived from 4,4,- Preparation of oxydiphthalic anhydride (= ODPA), 4,4 '· diaminophenyl ether (= 〇DA) and 2-hydroxyethyl methacrylate (R,) 5.90% by weight, corresponding to chemical formula 4bis Titanocene 20% NMP solution (component D) 5.10% by weight tetraethylene glycol dimethacrylate (component E) 0.07 reset% p-benzoquinone (component G) 0.68% by weight Silane adhesion promotion Agent (component J) 54.31% by weight N-methylpyrrolidone (component H) This composition was rolled overnight to produce a clear resin solution, and then filtered under pressure through a 0.2 micron hole width filter. The resin solution was spin-coated on silicon wafers and copper-coated silicon wafers, and then dried on a hot plate at 10 ° C for 5 minutes. In this way, a uniform thickness of 10 / m thick The polymer layer was paid on a circle. The wafer was then exposed to broadband spectral radiation using a Karl Suss MA 56 contact exposure tool. After exposure, the image was rotated by rotating the wafer at 1000 rpm and then Spray the wafer with cyclopentanone for 30 seconds, and then spray the wafer with equal volume of cyclopentanone and propylene glycol monomethyl ether acetate (pGMEA) at 1000 rpm for 10 seconds, and then use pure PGMEA It is sprayed for 15 seconds to develop. In the final step, the wafer is rotated at 2000 rpm for 30 seconds to dry. A high-quality convex image with 90% film is obtained on a silicon wafer, but a copper-coated wafer Not only the film retention rate of 10%, but also very poor pattern definition and adhesion loss. 0 19 556 045 V. Description of the invention (17 ^ Comparative Example 3 A negative photoresist composition was prepared by mixing the following: 38.30% by weight ♦ Sulfonate (component C), ^ is based on pyromellitic acid anhydride (= PMDA), 4,4'-diaminophenylphenyl (= 〇] 〇 ^ and 2-hydroxy Ethyl methacrylate (R,) is produced by 6.70 wt% 5.74 wt% ~ phase to 20% NMP solution (component D) of the titanium dioxide of chemical formula 41 (component D) tetraethylene glycol dimethyl propylene -0.08% by weight of p-benzoquinone (component G) --- 0.76% by weight of alkane adhesion promoter (component J)-48.42t *% ~ Ν-methylpyrrolidone (component η)

This composition was rolled overnight to produce a clear resin solution, and then filtered under pressure through a 0.2 micron hole width filter. The resin solution was spin-coated on a silicon silicon wafer and a copper-coated silicon wafer, and then dried on a hot plate of 105 t for 6 minutes. In this manner, a polymer layer with a uniform thickness of 15-17 // m is obtained on the wafer. The wafer was then exposed to broadband exposure using Karl Suss MA 56 exposure tool and an energy dose of 200 mJ / cm2. After exposure, the image was rotated by rotating the wafer at 1300 rpm and then spraying the wafer at qz · 2501 for 40 seconds. Thereafter, the same volume of qz-3501 and propylene glycol monomethyl ether acetate (PGMEA) and The wafer was sprayed at 3000 rpm for 15 seconds, and then developed at pure PGMEA and sprayed at 1300 rpm for 15 seconds. In the final step, the wafer is rotated to dryness at 3000 rpm. High-quality convex images were obtained on silicon wafers, but copper-coated wafers showed very poor pattern definition and almost no film retention. From the foregoing description of the invention, those skilled in the art will understand that the invention can be modified without departing from the spirit and scope thereof. Therefore, it is not intended that the scope of the invention be limited to the specific examples illustrated and described. 20 Public application dated case number category 6050F7 / ^ 4. (The above columns are filled out by this Office) n Amendment] Supplement A4 C4 556045 Installation line% ti Patent specification ___ Invention I, JCl: Name Chinese light Sensitive Polyimide Precursor Composition English PHOTOSENSITIVE POLYIMIDE PRECURSOR COMPOSITIONS One invention one, song • person name nationality residence, residence ⑴ Yamd Naini (2) Donald Reichart (3) Android J. Rocha (4) William D. Weber (5) Pamela J. Watson, United States 115 115 Warwick Love Road, Rhode Island, USA (2) 126 Fifth Street, Providence, Rhode Island, USA (3) No. 29 Barrington Peak Road, Rhode Island, United States of America gj, No. 1450, Lofood Portak Road, Rhode Island (5) North Bridge, Massachusetts, School No. 504- --- ^ " " Name (Name) American Businessmen • Aceh Specialty Chemicals Nationality US III. Applicant's Residence and Residence (Office) Representative No. 501 Norwalk Morrit, Connecticut, USA Name Sarah A. O'Connor Order 556045-V. Description of Invention (1) Technical Field of Invention For the invention-based polyimide for forming the light-sensitive composition of the precursor of the convex structure on the eve of the stone carrier circuits copper or silver, glass, ceramic or polymeric substrate studies. The light-sensitive composition according to the present invention is particularly suitable for microelectronic applications. BACKGROUND OF THE INVENTION Negative-tone light-sensitive polyfluorene imide precursors, mainly polyamidates containing a radiation-sensitive group in the ester portion, are known (USP 4,040,831; 4,548,891; and 6,010,825). When these polymers are formulated with a base photoinitiator and a crosslinking agent in a suitable solvent, the resulting material can be treated as a negative-tone photoresist. The light development and processability of these photoresist compositions can be improved by adding one or more compounds such as an adhesion promoter, a photosensitizer, a dye, a leveling agent, and a viscosity stabilizer to the composition. The final composition of this type is known and widely used in the microelectronics industry. Microelectronic applications include, but are not limited to, a stress convex layer, a protective coating, an alpha particle barrier coating, and a dielectric layer for packaging microelectronic devices. Substrate materials that have been treated with a light-sensitive polyimide coating include silicon element wafers, ceramics, glass, flexible polymer-metal foil, and the like. In use, the polyurethane composition is applied to the substrate as a thin film using any of a variety of coating methods (including spin, dip, spray, roll, meniscus, extrusion, and curtain coating). The formed wet film is heated at a temperature in the range of 50 to 150 t to provide a non-stick or soft-bake film. The soft-baked film is then exposed to actinic radiation at a wavelength in the range of 350 to 450 nm through a reticle. These actinic radiation are generally obtained from mercury lamps, with the most

5. Description of the invention (2) The rays used are i-line at 365 nm and g-line at 436 nm. Actinic rays interact with the photoinitiator in a photochemical reaction to produce an organic group, which initiates a crosslinking reaction between the polyurethane and the unsaturated group of the crosslinking agent. The products of this reaction have reduced solubility in certain solvents. Therefore, treating the exposed film with an appropriate solvent causes removal of the unexposed area and retention of the exposed area, and a convex pattern of the photomask is formed in the film. After the image is developed, the patterned polyimide film is converted into a patterned polyimide film by heating at a temperature in the range of 20 ° C to 450 ° C for a period of 30 minutes to 6 hours. Photochemistry The efficiency of cross-linking reactions in the production of insoluble products is known to be adversely affected by the presence of chemicals that react with the bases generated with photoinitiators. When the inhibition of the cross-linking effect occurs, the convex image is damaged or lost during the image development process, and the film loss during the development is high. A known example of this inhibitor is an oxygen molecule, which is Inhibit the photo-crosslinking effect of polyamide acrylate 'and is known as an inhibitor of the t-combination reaction of acrylates and acrylate derivatives. The inhibition of the cross-linking effect is also contained in certain organic Occurs when the light-sensitive polyfluorene imide precursor composition of the initiator is processed on a substrate in which a copper and silver metal layer is present. Reducing the soft baking temperature of the spin-coated coating can reduce the copper and silver Undesired restraint But 'this method reduces pattern resolution and causes unacceptable fast light rates and increased film losses. Increased industry use of copper and silver metals as conductors for semiconductor components, inductors, packages and flexible circuit components has been produced Demand for compositions with improved properties during which copper and silver layers are present.

V. Description of the invention (3) Summary of the invention The object of the present invention is to provide a negative-operation light-sensitive polyfluorene imide precursor composition whose photo-developing effect is applied to a copper or silver carrier substrate. And it is not inhibited when processing on it. The light-sensitive composition of the present invention is composed of a polyurethane polymer containing an ethylenically unsaturated group, a photocrosslinking additive, a photoinitiator, a metal inhibitor, a polymerization inhibitor, and a solvent. Optionally, and in addition to the foregoing components, the composition may contain one or more of a photosensitizer, an adhesion promoter, and a dye. Photosensitive compositions can be used in the manufacture of microelectronic devices and electronic applications such as thermal and mechanical stress buffer coatings, alpha particle barrier coatings, interlayer dielectric films, and as patterned engineering plastic layers . DETAILED DESCRIPTION OF THE INVENTION One aspect of the present invention is to provide a light-sensitive polyimide precursor composition comprising: (020-50 parts by weight of a polyimide polymer (C), The polycondensation of the diacid gaseous compound (A) and the diamine compound (B) yields 0 (ii) 1 to 4 parts by weight of the photoinitiator (D). (Iii) 3 to 10 parts by weight of the photoinitiator Crosslinking additive (E). (Iv) 0.005 to 1 part by weight of metal inhibitor (F). (V) 0.01 to 1 part by weight of polymerization inhibitor (G). (Vi) 44 to 76 parts by weight. Solvent (H). Optionally, and in addition to components A and D to Η (inclusive), the composition may contain one or more of the following components: # 3 556045 V. Description of the invention (8) | β ai And the group consisting of four ticks. This special agent can be used individually or in a mixture. In addition to the polymer A and the component magnet, the composition included in the present invention can optionally contain one of the following components or One or more of them are light sensitive _ which is selected from the group consisting of coumarins of chemical formula 5.

Ra (Chemical Formula 5) wherein I and R4 are each a CVC6 alkyl group, and Rs represents a Ci-C6 alkylcarbonyl group, a CVC6 alkoxycarbonyl group, a C6_Ci4 arylcarbonyl group, or a " aryloxycarbonyl group, which is optionally HCk Alkylamino substituents. One or more adhesion-promoting compounds (j) are selected from the group consisting of amine alkoxy sulphuric acid and amine alkoxy silane derivatives. The formulated composition may also contain additives such as colorants, colorants, fillers, adhesives, wetting agents, and dyes, which can affect the spectral sensitivity of the mixture by its characteristic absorption. In the first step of applying the light-sensitive polyfluorene imide precursor composition contained in the present invention, the light-sensitive composition is applied to a substrate such as a silicon element wafer, a Tao Yao substrate, or a flexible polymer substrate. On a substrate such as this, it may have a copper or silver metal coated or attached by an adhesive. Applicable coating methods include spin coating, roll coating, offset printing, screen printing, 11 V. Description of the invention (9) Extrusion coating, meniscus coating, dip coating and spray coating Cover, but not limited to this. The formed wet coating is dried at 70 to 150 ° C using a hot plate, convection oven, belt furnace, etc. for a period of several minutes to 12 hours, depending on the coating method and film thickness. . The dry coating is exposed to actinic radiation through the shield pattern in such a way that the image of the shield pattern is formed on a dry film. Examples of actinic radiation used in the practice of the present invention are x-rays, electron beams, ultraviolet rays, and visible rays. The best rays are those with a wavelength of 365 nm & 436 nm and can be easily obtained from a mercury lamp source. In the next step, the film with an image is developed to form a convex image of a shield pattern by treating the exposed film with a suitable solvent. Examples of the solvent used in the practice of the present invention include butyrolactone, "pyrrolidone, n-butyl acetate, ethyl lactate, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, isopropyl alcohol, and the like A mixture of two or three, but not limited to this. Image development can be 70% by a similar method already used in dipping, spraying, mixing, spray-mixing, or other photoresist techniques. The convex pattern of the development is suitable for moving In addition to developer solvents, solvent washing. The washing solvents used in the practice of the present invention include n-butyl acetate, propylene glycol monoethyl acetate, and isopropanol, but are not limited to this. However, 'convex image through 200 to 425. The temperature is in the range of 30 minutes to 6 μ, and it is transformed into a patterned polyimide film.

Claims (1)

556045 VI. Application for Patent Scope No. 90115270 Patent Application for Amendment of Patent Scope 1. A light-sensitive polyfluorene imide precursor composition containing a polyamine ester polymer, which is prepared by using at least one diesteric acid Obtained by polycondensation of a gaseous compound with at least one diamine compound; a titanocene photoinitiator; a photocrosslinkable additive; a metal inhibitor selected from the group consisting of 1H-tetrafluorene and 1,2-cyclohexane A diamine tetraacetic acid hydrate and 5-mercaptobenzimidazole; a polymerization inhibitor; a solvent; and one or more of the following: at least one photosensitizer compound; and at least one adhesion promoting compound. 2. The light-sensitive polyfluorene imide precursor composition according to item 1 of the patent application, wherein the titanocene photoinitiator is selected from bis (· β 5-2, cyclopentadien-1-yl ) -Bis (2,6-difluoro-3 · (1Η-solo-1-yl) phenyl) titanium, and bis (methylcyclopentadienyl) -bis (2,6 · difluorobenzene_ Μ-based) titanium. 3. · A method for photochemical crosslinking of a photosensitized polyfluorene imide precursor composition in the presence of a titanocene photoinitiator and a metal selected from copper and silver, the improvement comprising The polyimide precursor composition contains a metal inhibitor selected from the group consisting of 1-tetrazole, 1,2-cyclohexanediamine tetraacetate hydrate, and 5-mercaptobenzimidazole to reduce photochemical crosslinking Of inhibition. Size of this paper ¥ Use towel Country :: Standard (CNS) A4rfT2i〇x297 public Chu) ------ 556045 AB c D VI. Application for patent scope 4. A kind of light reduction in the presence of a metal selected from copper and silver The method for inhibiting the photochemical cross-linking of a sensitive polyimide precursor composition includes an improvement of the polyimide precursor composition including the photochemical cross-linking application patent item 1. 5. · A method for reducing the photochemical crosslinking inhibition of a photosensitized polyimide precursor composition in the presence of a metal selected from the group consisting of copper and silver, and the improvement includes the second item in the scope of patent application for photochemical crosslinking Polyimide precursor composition. This paper size applies to China National Standard (CNS) A4 (210X297 mm)