TW556045B - Photosensitive polyimide precursor compositions - Google Patents
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五、發明說明(4) (νιι)0.1-2.0份重量之一或多種之光敏感劑化合物(1)。 〇111)0.05-2.0份重量之黏著促進化合物(】)。 聚醯胺酯聚合物(C)具有5至1〇〇之數平均聚合度,且 係藉由如下之(1)以單體A&B之聚縮合反應而合成··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 ...
單體A係藉由二酐化合物與醇r,〇h之反應而獲得, 以產生二酯_二酸,其後藉由適當試劑使二酸_二酯轉化成 二酯-二酸氯化物(化學式2)。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).
(化學式2) R基表示含有至少一6-元碳環之四價芳香族基,其中 四羰基係直接連接至R之不同碳原子,且其中二對之四幾 基之每一者係連接至相鄰之碳原子。二酐化合物可選自下 述二酐之一或多者:均苯四酸二酐(pMDA)、3,3,,4,4、一 苯甲酮四羧酸二酐(BTDA)、3,3,,4,4,-雙苯基四竣酸二 556045 五、發明說明(5) (BPDA)、3,3,,4,4,-二苯基颯四羧酸二酐、4,4,_全氟異丙 叉基二酞酸二酐(6FDa)、4,4,-氧二酞酸酐(ODPA)、雙(3,4· 二羧基)四甲基二矽氧烷二酐、雙(3,4-二羧基苯基)二甲基 石夕燒二酐、環丁烧四羧酸二酐,及1,4,5,8_萘四羧酸二酐。 四羧酸二酐可單獨或混合使用,且二酐化合物之選擇不限 於上示化合物。R’基含有至少一不飽和基,其可為乙烯基、 稀丙基、丙烯基、甲丙烯基、炔基、氰基,或其它適合之 可輻射交聯之基。 單體B係二價二胺,其中Rl基係含有至少一個6_元碳 環’且係選自下列基之至少一者:二價芳香族、雜環、脂 環或脂肪族胺:間-苯二胺、對-苯二胺、2,2,_雙(三氟甲 基)-4,4,-二胺基-1、丨,_聯苯、3,4、二胺基二苯基醚、4,4、 一胺基二苯基醚、3,3’·二胺基二苯基醚、2,4-甲苯二胺、 3,3’-二胺基二苯基颯、3,4,-二胺基二苯基颯、4,4,-二胺 基二苯基颯、3,3,-二胺基二苯基甲烷、4,4,_二胺基二苯 基甲烷、3,3’-二胺基二苯基甲烷、3,4,_二胺基二苯基甲 烷、4,4,-二胺基二苯基酮、3,3、二胺基二苯基酮、3,4,_ 二胺基二苯基酮、1,3-雙(4-胺基苯氧基)苯、i,3•雙(3_胺 基-苯氧基)苯、1,4-雙(7_胺基丙基)四甲基二矽氧烷、 253,5,6-四曱基-對-苯二胺、間_苯二甲胺、對_苯二甲胺、 曱二胺、四甲撐基二胺、五甲撐基二胺、六甲撐基二胺、 2,5-—曱基六甲撐基二胺、3-甲氧基六曱撐基二胺、七甲 撐基二胺、2,5-二甲基七甲撐基二胺、3_甲基七甲撐基二 胺、4,4_二甲基七甲撐基二胺、八曱撐基二胺、九曱撐基 556045 五、發明說明(6) 二胺、2,5-二甲基九曱撐基二胺、十甲撐基二胺、乙二胺、 丙二胺、2,2-二甲基丙二胺、1,10-二胺基-ΐ,ι〇-二甲基癸 烷、2,110二胺基十二烷、1,12-二胺基十八烷、2,17_二胺 基二十烷、3,3,-二甲基-4,4,-二胺基二苯基甲烷、雙(4·胺 基環己基)甲烷、3,3,_二胺基二苯基乙烷、4,4’-二胺基二 苯基乙稀,及4,4、二胺基二苯基硫化物、2,6-二胺基0比σ定、 2,5-二胺基吡啶、2,6-二胺基-4-三氟甲基吡啶、2,5-二胺 基_1,3,‘噁二唑、1,4·二胺基環己烷、哌嗪、4,4,-曱撐基 二苯胺、4,4’-甲撐基·雙(鄰-氯苯胺)、4,4’-甲撐基-雙(3_ 甲基苯胺)、4,4,-甲撐基-雙(2_乙基苯胺)、4,4,-甲撐基-雙 _(2-甲氧基苯胺)、4,4,-氧-二苯胺、4,4,-氧-雙(2-甲氧基笨 胺)、4,4’-氧·雙(2-氣苯胺)、4,4,-硫基-二苯胺、4,4,-硫基 •雙-(2-甲基苯胺)、4,4,-硫基-雙-(2-甲氧基苯胺)、4,4,-疏 基-雙-(2-氣苯胺)、3,3,-磺基-二苯胺、3.3,_磺基_二苯胺。 單體Β之選擇係受限於此等化合物,且單體β可單獨或現 合使用。 光起始劑D係選自下述所組成之族群之至少一者: 化學式3 化學式4(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
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五、發明說明(7) 即,雙(77.5_2,4_ 環戊二烯 _;!_ 基)_雙(2,6_ 二氟 _3_(ih_ 响咯-i-基)苯基)鈦,及雙(曱基環戊二烯基)_雙(26_二氟 本-1-基)欽。 光交聯劑(E)係選自選自下述所組成之族群之至少一 者:丙烯酸或甲基丙烯酸及芳香族及特別之具有2-3(H@c 原子之脂肪族多元醇或5或6個C碳原子之環脂族多元醇之 酯及部份酯。適當組份(E)之例子係··丙二醇二丙烯酸酯、 乙二醇二甲基丙烯酸酯、二乙撐二醇二丙烯酸酯、二乙撐 二醇二曱基丙烯酸酯、三甲撐二醇二丙烯酸酯、三甲撐二 醇二曱基丙烯酸酯、四乙撐二醇二丙烯酸酯、四乙撐二醇 一曱基丙烯酸S旨、具200-2 000範圍之平均分子量之聚乙撐 二醇二(甲基)丙烯酸酯、具500-15 〇〇〇範圍之平均分子量 之二曱基醇丙烧乙醇醋三(曱基)丙稀酸醋、季戊四醇三(甲 基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、季戊四醇四(甲 基)丙稀酸酯等。 金屬抑制劑化合物(F)係選自下述所組成之族群之至 少一者·· 1H-四唑、1,2-環己烷二胺四乙酸水合物,及% 疏基本弁嗦σ坐。 聚合反應抑制劑(G)係選自對-苯并醌酮、硫基二苯基 胺及烷基醇(諸如,4_第三丁基酚、2,5-二-第三丁基氫醌 或2,6-二-第三丁基_4_曱基酚)所組成之族群。 溶劑(Η)係選自2_甲基吡咯烷酮、7 - 丁内酯、Ν,Ν-二 甲基甲醯胺、Ν,Ν-二曱基乙醯胺、二甲基硫氧化物、環 丁楓、乙二醇單曱基醚、環戊酮、丙二醇單甲基醚乙酸酯 10 556045 五、發明說明(10) 範例1 負光阻組成物,其係藉由混合下述而製備·· 37.03重量% 聚醯胺酸酯(組份C),其係自4,4,-氧二酞 酸酐(=ODPA)、4,4,-二胺基苯基醚(=〇da) 及2-經基乙基甲基丙稀酸醋(R’)製備 重量% 相對應於化學式3之二茂鈦(組份D) 5 · 3 6重量% 四乙撐基二醇二甲基丙烯酸酯(組份E) ^5重量% ίΗ·四唑(組份F) 〇.〇7重量% ^士-苯醌(組份G) 重量% 矽烷黏著促進劑(組份J) 2.25重量% Ν-甲基吡咯烷酮(組份Η)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)
此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 微米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 裸矽晶圓及被塗覆之矽晶圓上,然後,於1〇〇。〇之熱板上 乾燥7分鐘。以此方式,11 # m厚之均勻厚度之膜於晶圓 上獲得。然後,使用Canon 300i i-線步級器(stepper)曝照 工具使晶圓曝照於具365nm波長之單色光。曝照後,影像 藉由以1000 rpm旋轉晶圓及然後以環戊酮噴灑晶圓35秒, 其後同時以等體積之環戊酮及丙二醇單甲基醚乙酸酯 (PGMEA)且以1000 rpm喷灑晶圓10秒鐘,然後以純PGMEA 喷灑15秒鐘而顯影。最後步驟,晶圓以3000 rpm旋轉至乾 燥。高品質之凸影像於矽晶圓及以銅塗覆之矽晶圓上獲 得。用以於二基材上顯影後獲得90%之被保持膜厚度所需 之曝照劑量係300 mJ/cm2。 13 556045This 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
五、發明說明(u) 範例2 負光阻組成物,其係藉由混合下述而製備: 37.34重量% 聚酿胺酸S旨(組份C),其係自4,4’ -氧二欧 酸酐(=ODPA)、4,4,-二胺基苯基醚(=〇DA) 及2-羥基乙基甲基丙烯酸酯(R,)製備 6.54重量% 相對應於化學式4之二茂鈦之20%NMP溶 液(組份D) 5.61重量% 四乙撐基二醇二曱基丙烯酸酯(組份E) 0.0 5重量% 1H-四唑(組份F) J3.07重量% 177¾ 醌(組份G) ' " ^〇.74重量% 矽烷黏著促進劑(組份J) 49.64重量% N-甲基吡咯烷酮(組份η) 此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 U米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 裸矽晶圓及以銅塗覆之矽晶圓上,然後,於10(rc之熱板 上乾燥7分鐘。以此方式,11# m厚之均句厚度之膜於晶 圓上獲得。然後,使用Canon 300i i-線步級器曝照工具使 晶圓曝照於具365nm波長之單色光。曝照後,影像藉由以 1〇〇〇 rpm旋轉晶圓及然後以環戊酮噴灑晶圓35秒,其後同 時以等體積之環戊酮及丙二醇單甲基醚乙酸酯(pGMEA) 且以1000 rpm噴灌晶圓1〇秒鐘,然後以純pgmeA喷丨麗15 移叙而顯影。最後步驟,晶圓以3000 rpm旋轉至乾燥。高 口口夤之凸影像於矽晶圓及以銅塗覆之矽晶圓上獲得。形成 90%之被保持膜厚度之曝照劑量對矽晶圓係12〇 mJ/cm2, 且對銅晶圓係140 mJ/cm3。 556045V. 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
範例3 負光阻組成物,其係藉由混合下述而製備: 26.44Ϊ*%~~ 酸酯(組份C),其係二酞 酸酐(=ODPA)、4,4,·二胺基苯基醚卜〇da) 及2-羥基乙基甲基丙烯酸酯(R,)贺借 0.93重量% 相對應於化學式3之二茂鈦(組份D) _ 3 · y 7重置% 四乙#基二醇二曱基丙稀酸酯(組份E) 0.034重置% h2-環己烷二胺四乙酸酐(組份F) 0.053重量% 身-苯醌(組份G) CDAC(組份 I) 0 · 5 3重置% 矽烷黏著促進劑(組份J) 33.98重量% (組份H) — 33.98重量% Ν-甲基吡咯烷酮(組份η) 此組成物被滾動隔夜而產生澄清樹脂溶液,然後接 叉加壓過濾。樹脂溶液被旋轉塗覆於銀塗覆之矽晶圓上, 然後,於100°c之熱板上乾燥2分鐘。以此方式,4.5//m 厚之均勻厚度之膜於晶圓上獲得。然後,晶圓使用Karl Suss ΜΑ 56接觸曝照工具且以3〇〇 mJ/cm2之能量劑量被曝照於 寬帶譜輻射。曝照後,影像藉由以1 〇〇〇 rpm旋轉晶圓及然 後以環戊酮噴灑晶圓10秒,其後同時以等體積之環戊酮及 丙二醇單曱基醚乙酸酯(PGMEA)且以1000 rpm喷灑晶圓10 秒鐘,然後以純PGMEA噴灑10秒鐘而顯影。最後步驟, 晶圓以3000 rpm旋轉至乾燥。高品質之凸影像於以銀塗覆 之矽晶圓上獲得,且具有70%之膜厚度保持。 15 556045 五、發明說明(13 ) 範例4 負光阻組成物,其係藉由混合下述而製備·· 38.28重量% 份 c),其 酐(=PMDA)、4,4’_二胺基苯基鱗(=〇DA) 及2-羥基乙基甲基丙烯酸酯借 6.7 0 重量 °/〇 相對應於化學式4之二茂鈦之2〇%NMP溶 液(組份D) 5.74重置% 四乙撐基二醇二甲基丙稀酸酯(組份 0·05重置% 1H-四嗤(組份ρ) 0.08重里% 組份 g) " ~-- 0 · 7 6重。里% 矽烷黏著促進劑(組份J) 48.39重量% N-甲基吡咯烷酮(組份η) ' 此組成物被滾動隔夜而產生澄清樹脂溶液,然後經〇.2 微米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 裸矽晶圓及以銅塗覆之矽晶圓上,且晶圓於l〇5cc之熱板 上乾燥6分鐘。以此方式,15至17/zm厚之均勻厚度之聚 合物層於晶圓上獲得。然後,晶圓使用Kari Suss μα 56 接觸曝照工具且以200 mJ/cm2之能量劑量被曝照於寬帶譜 輻射。曝照後,影像藉由以1300 rpin旋轉晶圓及然後以 QZ-3501噴灑晶圓40秒,其後同時以等體積之〇2_35〇1及 丙二醇單甲基醚乙酸酯(pGMEA)且以3〇〇〇 rprn喷灑晶圓15 秒鐘,然後以純PGMEA且以1300 rpm喷灑15秒鐘而顯影。 最後步驟,晶圓以3000 rpm旋轉至乾燥。高品質之凸影像 於矽晶圓及以銅塗覆之矽晶圓上獲得。 16 556045 五、發明說明(14) 範例5 負光阻組成物,其係藉由混合下述而製備: 38.28重量。/〇 聚醯胺酸酯(組份C),其係自均苯四酸二 酐(=PMDA)、4,4,-二胺基苯基醚(=〇DA) 及2 -經基乙基甲基丙稀酸醋(R )製備 丄二34重量% 相對應於化學式3之二茂鈦(組份D) 5.7 4重量% 四乙撐基二醇二甲基丙烯酸酯(組份E) 〇·〇5重量% 1H-四唑(組份F) 0.08重量% 對-苯醌(組份G) 〇·76重量% 黏著促進劑(組份J) 53.75重量% N-甲基吡咯烷酮(組份H) 此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 微米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 Cu塗覆之矽晶圓上,然後,於1〇5。〇之熱板上乾燥1〇分鐘。 以此方式,30至35//m厚之均勻厚度之聚合物層於晶圓上 獲付。然後’晶圓使用Karl Suss MA 56接觸曝照工具且 以500 mJ/cm2之能量劑量被曝照於寬帶譜輻射。曝照後, 影像藉由以1300 rpm旋轉晶圓及然後以qZ_35〇1喷灑晶圓 80秒,其後同時以等體積之qZ_3501及丙二醇單甲基喊乙 酸酯(PGMEA)且以3000 rpm喷灑晶圓15秒鐘,然後以純 PGMEA且以1300 rpm喷灑15秒鐘而顯影。最後步驟,晶 圓以3000卬m旋轉至乾燥。高品質之凸影像於以銅塗覆之 矽晶圓上獲得。500 mj/cm2之曝照能量造成自原始軟式焙 烤膜厚度顯影後之89.1%之膜保持率。 556045 五、發明說明(15) 比較例1 負光阻組成物,其係藉由混合下述而製備: 37.01重量% 聚醯胺酸酯(組份C),其係自4,4,-氧二酞 酸酐(=ODPA)、4,4,·二胺基苯基醚(=〇da) 及2-羥基乙基甲基丙烯酸酯(R,)製備 1.3重量% 相對應於化學式3之二茂鈦(組份D) 5.56重篁% 四乙撐基二醇二甲基丙烯酸酯(組份幻 0.07重量% 對-苯醌(組份G) 0.74重量% 矽烷黏著促進劑(組份J) 55.32重量% 基吡咯烷酮(組份H) 此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 你支米孔洞寬度之過濾器加壓過滤。樹脂溶液被旋轉塗覆於 裸石夕晶圓及以銅塗覆之石夕晶圓上,然後,於1 〇5。〇之熱板 上乾燥8分鐘。以此方式,20 # m厚之均勻厚度之聚合物 層於晶圓上獲得。然後,使用Canon 3〇〇i卜線步級器曝照 工具使晶圓曝照於具365nm波長之單色光。曝照後,影像 藉由以1000 rpm旋轉晶圓及然後以環戊酮喷灑晶圓7〇秒, 其後同時以等體積之環戊酮及乙酸正丁酯(NBA)且以1〇〇〇 rPm噴灑晶圓1〇秒鐘,然後以純NBA噴灑1〇秒鐘而顯影。 最後步驟,晶圓以3000 rpm旋轉至乾燥。高品質之凸影像 於矽晶圓上獲得,且於410 mJ/cm2之曝照能量具有91%之 膜厚度保持率。銅晶圓顯示具差的黏著性之非常差之界定 圖案,及具17%膜厚度保留率之大量膜喪失。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 五、發明說明(l6) 比較例2 負光阻組成物,其係藉由混合下述而製備: 33.94重量% 聚醯胺酸酯(組份C),其係自4,4,-氧二酞 酸酐(=ODPA)、4,4’·二胺基苯基醚(=〇DA) 及2_羥基乙基甲基丙烯酸酯(R,)製備 5.90重量% 相對應於化學式4之二茂鈦之20%NMP溶 液(組份D) 5.10重量% 四乙撐基二醇二甲基丙烯酸酯(組份E) 0.07重置% 對·苯醌(組份G) 0.68重量% 矽烷黏著促進劑(組份J) 54.31重量% N-甲基吡咯烷酮(組份H) 此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 微米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 矽晶圓及以銅塗覆之矽晶圓上,然後,於1〇(rc之熱板上 乾燥5分鐘。以此方式,1〇//m厚之均勻厚度之聚合物層 於b曰圓上獲付。然後’晶圓使用Karl Suss MA 56接觸曝 照工具被曝照於寬帶譜輻射照射。曝照後,影像藉由以1〇〇〇 rpm旋轉晶圓及然後以環戊酮喷灑晶圓3〇秒,其後同時以 等體積之環戊酮及丙二醇單甲基醚乙酸酯(pGMEA)且以 1000 rpm喷灑晶圓1〇秒鐘,然後以純PGMEA喷灑15秒鐘 而顯影。最後步驟,晶圓以2〇〇〇 rpm旋轉3〇秒至乾燥。 具90%膜之高品質凸影像於矽晶圓上獲得,但以銅塗覆之 晶圓顯不僅10%之膜保持率及非常差之圖案界定及黏著損 失0 19 556045 五、發明說明(17 ^ 比較例3 負光阻組成物,其係藉由混合下述而製備: 38.30重量% ♦醯胺酸酯(組份C),^係自均苯四酸一 酐(=PMDA)、4,4’-二胺基苯基驗(=〇]〇^ 及2-羥基乙基甲基丙烯酸酯(R,)製借 6.70重量% 5.74重量%~ 相到應於化學式41二茂鈦之2〇%NMP溶 液(組份D) 四乙撐基二醇二甲基丙一- 〇. 0 8重量% 對-苯醌(組份G) --- 0.76重量% 每烷黏著促進劑(組份J)-- 48.42t *%~ Ν-甲基吡咯烷酮(組份η)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)
此組成物被滾動隔夜而產生澄清樹脂溶液,然後經0.2 微米孔洞寬度之過濾器加壓過濾。樹脂溶液被旋轉塗覆於 鐘矽晶圓及以銅塗覆之矽晶圓上,然後,於1 〇5 t之熱板 上乾燥6分鐘。以此方式,15-17//m厚之均勻厚度之聚合 物層於晶圓上獲得。然後,晶圓使用Karl Suss MA 56接 觸曝照工具且以200 mJ/cm2之能量劑量被曝照於寬帶譜輻 射。曝照後,影像藉由以1300 rpm旋轉晶圓及然後以qz· 2501喷灑晶圓40秒,其後同時以等體積之qz-3501及丙二 醇單甲基醚乙酸酯(PGMEA)且以3000 rpm喷灑晶圓15秒 鐘,然後以純PGMEA且以1300 rpm噴灑15秒鐘而顯影。 最後步驟,晶圓以3000 rpm旋轉至乾燥。高品質凸影像於 矽晶圓上獲得,但以銅塗覆之晶圓顯示非常差之圖案界定 及幾乎無膜保留。 藉由本發明之前述描述,熟習此項技藝者會瞭解在 未偏離其精神及範圍下可對本發明作改良。因此,不欲使 本發明範圍受限於所例示及描述之特殊具體例。 20 公本 申請曰期 案 號 類 别 6〇5F7/^4. (以上各欄由本局填註) n 修正] 補充 A4 C4 556045 裝 線 % ti專利説明書 ___ 發明 一、JCl:名稱 中文 光敏感性聚醯亞胺前驅物組成物 英 文 PHOTOSENSITIVE POLYIMIDE PRECURSOR COMPOSITIONS 一發明 一、麯•人 姓 名 國 籍 住、居所 ⑴亞姆德•奈尼 (2) 唐納德•雷希卡特 (3) 安卓J.羅查 (4) 威廉D.韋伯 (5) 帕米拉J.瓦特森 美國 ⑴美國羅德島州瓦威克·愛情路115號 (2) 美國羅德島州普羅維登斯·第五街126號 (3) 美國羅德島州巴林頓•山頂道29號 gj养國羅德島州魯佛德•波塔克特道145〇號 (5)美國麻州北橋•學校衔5〇4號 -----^ "" 姓 名 (名稱) 美商·亞契專業化學公司 國 籍 美國 三、申請人 住、居所 (事務所) 美國康乃狄克州諾渥克·莫理特501號 代表人 姓 名 莎拉A.歐康諾 訂 556045 -- 五、發明說明(1 ) 發明之技術領域 本發明係有關用於在承載銅或銀電路之石夕、玻璃、陶 究或聚合物基材上形成凸結構之光敏感性聚醯亞胺前驅物 組成物。依據本發明之光敏感性組成物係特別適於微電子 學之應用。 發明之技術背景 以於酯部份含有輻射敏感性基之聚醯胺酯為主之負 色調光敏感性聚醯亞胺前驅物係已知(USP 4,040,831 ; 4,548,891 ;及6,010,825)。當此等聚合物於適當溶劑内與 基光起始劑及交聯劑配製時,形成之材料可作為負色調光 阻物而處理。此等光阻組成物之光顯像及可加工處理性可 藉由於此組成物添加一或多種諸如黏著促進劑、光敏感 劑、染料、均染劑及黏度安定劑之化合物而改良。此型式 之终多組成物係已知,且被廣泛用於微電子產業。微電子 應用包含封裝微電子裝置之應力凸層、保護塗覆物、α顆 粒障壁塗覆物,及作為介電層,但不限於此。已以光敏感 性聚醯亞胺塗覆物處理之基材材料包含矽元件晶圓、陶 瓷、玻璃、可撓性聚合物-金屬箔等。 使用中,聚醯胺酯組成物係使用任何各種塗覆方法(包 含旋轉、浸潰、噴灑、滚軋、彎液面、擠塑及帘幕塗覆) 而以薄膜塗覆於基材上。形成之濕膜於50至1 5〇t範圍之溫 度加熱,以提供無黏性或,,軟式焙烤,,之薄膜。然後,軟式 焙烤之薄膜被曝照於經光罩之350至450 nm範圍之波長之 光化輻射作用。此等光化輻射一般係自汞燈獲得,其最有 556045This 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
五、發明說明(2) 用之射線係365 nm之i-線及436 nm之g-線。光化射線於光 化學反應内與光起始劑產生相互作用,產生有機基,其起 始聚醯胺酯與交聯劑之不飽和基之基交聯反應。此反應之 產物具有於某些溶劑内之降低可溶性。因此,以適當溶劑 處理被曝照之膜造成未被曝照區域之移除及被曝照區域之 保留,而於膜内形成該光罩之凸圖案。於影像顯影後,具 圖案之聚醯胺酯膜藉由於20(TC至450°C範圍之溫度施熱持 續30分鐘至6小時範圍之時間而轉化成具圖案之聚醯亞胺 膜。 光化學交聯反應於生產不可溶產物之效率已知係藉 由與以光起始劑而產生之基反應之化學品之存在而受不利 影響’其係以諸如避免或抑制聚合物之交聯作用之方式而 為之。當對交聯作用之抑制產生時,凸影像於影像顯影處 理期間受損或喪失,且顯影期間之膜損失係高。此一抑制 劑之已知例子係氧分子,其係抑制聚醯胺丙烯酸酯之光交 聯作用’且係已知作為對丙烯酸酯及丙烯酸酯衍生物之基 t合反應之抑制劑。對交聯作用之抑制亦於含某些有機二 茂欽光起始劑之光敏感性聚醯亞胺前驅物組成物於其間銅 及銀金屬層存在之基材上被處理時發生。降低旋轉塗敷塗 覆物之軟式焙烤溫度可減少對銅及銀層之非所欲抑制作 用。但是’此方法減少圖案解析,且造成不可接受之快速 光速率及增加之膜損失。增加之產業使用銅及銀金屬作為 半導體元件、感應器、封裝物及可撓性電路元件之導體已 產生具改良性能之其間銅及銀層存在之組成物之需求。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.
五、發明說明(3 ) 發明之概要描述 本發明之目的係提供一種負操作光敏感性聚醯亞胺 前驅物組成物,其光顯影作用於組成物被塗敷至銅或銀承 載基材上及於其上處理時係不被抑制。本發明之光敏感性 組成物係由含有乙烯不飽和基之聚醯胺酯聚合物、光交聯 添加劑、光起始劑、金屬抑制劑、聚合抑制劑及溶劑所組 成。選擇性地,且除前述組份外,組成物可含有一或多種 之光敏感劑、黏著促進劑及染料。 光敏感性組成物可被用於微電子裝置之製造及電子 應用,諸如,熱及機械應力緩衝塗覆物、α顆粒障壁塗覆 物、層間之介電膜,及作為具圖案之工程塑膠層。 發明之詳細描述 本發明一方面係提供一種光敏感性聚醯亞胺前驅物 組成物,其包含: (020-50份重量之聚醯胺酯聚合物(C),其係藉由二酯_ 二酸氣化物化合物(Α)與二胺化合物(Β)之聚縮合作用而獲 得0 (ii) l-4份重量之光起始劑(D)。 (iii) 3-10份重量之可光交聯之添加劑(E)。 (iv) 0.005-l份重量之金屬抑制劑(F)。 (v) 0.01-l份重量之聚合反應抑制劑(G)。 (vi) 44-76份重量之溶劑(H)。 選擇性地,及除組份A與D至Η(包含)外,組成物可含 有下述組份之一或多者: #3 556045 五、發明說明(8) |β ai 及四虱吱喃所組成之族群。 砰此專洛劑可個別或以混合物使 用。 除聚合物A及組份磁外,由本發明包含之組成物可 選擇性地含有下述組份之一或多者。 一或多者之光敏感_其係選自化學式5之香豆素所 組成之族群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 (化學式5) 其中I及R4彼此係CVC6烷基,且Rs表示Ci-C6烷基羰 基、CVC6烷氧基羰基、C6_Ci4芳基羰基,或"芳氧基 羰基,其選擇性地HCk二烷基胺基取代基取代。 一或多者之黏著促進化合物(j),其係選自胺基烷氧基 石夕烧及胺基烷氧基矽烷衍生物所組成之族群。 配製之組成物亦可含有添加劑,諸如,色料、著色劑、 填料、黏著劑、濕化劑及染料,其可藉由其特性吸收性影 響混合物之光譜敏感性。 於塗敷本發明所包含之光敏感性聚醯亞胺前驅物組 成物之第一步驟,光敏感性組成物係被塗覆於諸如矽元件 晶圓、陶堯基材、可撓性聚合物基材等之基材上,其可具 有藉由黏著劑而對其塗覆或附接之銅或銀金屬。適用之塗 覆方法包含旋轉塗覆、滚軋塗覆、偏移印刷、篩屏印刷、 11 五、發明說明(9 ) 擠塑塗覆、彎液面塗覆、浸潰塗覆及喷灑塗覆,但不限於 此。形成之濕塗覆物係於70至150°C之溫度使用熱板、對流 爐、帶式爐等乾燥或軟式烘烤數分鐘至12小時之時間,其 係依塗覆方法及膜厚度而定。乾燥塗覆物係以使屏蔽罩圖 案之影像於乾燥膜形成之方式曝照於經屏蔽罩圖案之光化 輻射。用於本發明實施之光化輻射之例子係χ_射線、電子 束、紫外線及可見光射線。最佳之射線係具365 nm&436 nm之波長者,且可自汞燈源輕易獲得。 於下一步驟,具影像之膜藉由以適當溶劑處理被曝照 之膜而顯影形成屏蔽罩圖案之凸影像。用於實施本發明之 溶劑之例子包含卜丁内酯、”基吡咯烷酮、乙酸正丁 酯、乳酸乙酯、環戊酮、環己酮、丙二醇單甲基醚乙酸酯、 異丙醇及其二或三者之混合物,但不限於此。影像顯影可 ^由浸漬、噴灑、攪煉、噴灑-攪煉或其它光阻物技藝中已 之相似方法70成。顯影之凸圖案以適於移除顯影劑溶劑 ^溶劑沖洗。用於本發明實施之沖洗溶劑包含乙酸正丁 6曰、丙二醇單乙基職乙酸醋,及異丙醇,但不限於此。然 ,’凸影像藉由於200至425。。範圍之溫度施熱3〇分鐘至6 μ時範圍之時間而轉化成具圖案之聚醯亞胺膜。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.
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