TWI782241B - Polyimide positive photoresist composition - Google Patents
Polyimide positive photoresist composition Download PDFInfo
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- TWI782241B TWI782241B TW108140948A TW108140948A TWI782241B TW I782241 B TWI782241 B TW I782241B TW 108140948 A TW108140948 A TW 108140948A TW 108140948 A TW108140948 A TW 108140948A TW I782241 B TWI782241 B TW I782241B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
Description
本揭露關於一種聚醯亞胺正型光阻組成物,尤指一種以其製備的光阻膜具有良好耐化特性的聚醯亞胺正型光阻組成物。 The present disclosure relates to a polyimide positive photoresist composition, especially a polyimide positive photoresist composition with good chemical resistance for a photoresist film prepared therefrom.
於電子裝置(例如,功率元件、顯示裝置、觸控裝置、半導體裝置)之製備過程中,向來以正型或負型等各種光阻組成物作為材料,並利用其感光特性進行圖案化以及硬化該些光阻組成物以形成鈍化層、保護層、或絕緣層等構件。 In the manufacturing process of electronic devices (such as power components, display devices, touch devices, semiconductor devices), various photoresist compositions such as positive or negative have been used as materials, and their photosensitive properties are used for patterning and hardening These photoresist compositions are used to form components such as passivation layer, protective layer, or insulating layer.
光阻組成物的種類非常多種,其中一種為聚醯亞胺正型光阻組成物。目前已知的聚醯亞胺正型光阻組成物需要在300℃以上的高溫固化,但高溫固化產生的熱應力較大,可能發生基板翹曲、黏合強度降低、破壞其下層疊構影響下層耐電壓特性。 There are many kinds of photoresist compositions, one of which is polyimide positive photoresist composition. The currently known polyimide positive-type photoresist composition needs to be cured at a high temperature above 300°C, but the thermal stress generated by high-temperature curing is relatively large, and the substrate may warp, reduce the adhesive strength, and destroy the underlying layer structure and affect the underlying layer. withstand voltage characteristics.
此外,一般的聚醯亞胺正型光阻組成物在固化後還會殘留-OH或-COOH,使得所形成的光阻膜的耐化特性不佳。因此,當於光阻膜上形成金屬圖案(例如:電極、線路或其他)時,所使用的鹼性光阻剝離劑(stripper)會破壞光阻膜,而導致產品的良率或使用率降低。 In addition, the general polyimide positive photoresist composition still has residual -OH or -COOH after curing, which makes the chemical resistance of the formed photoresist film poor. Therefore, when metal patterns (such as electrodes, lines or others) are formed on the photoresist film, the alkaline photoresist stripper (stripper) used will damage the photoresist film, resulting in lower product yield or utilization rate. .
因此,目前須發展一種可於低溫下固化且固化後能展現良好耐化特性的聚醯亞胺正型光阻組成物。 Therefore, it is necessary to develop a polyimide positive photoresist composition that can be cured at low temperature and exhibit good chemical resistance after curing.
本揭露之主要目的在於提供一種聚醯亞胺正型光阻組成物,其除了可在低溫固化外,所得到的光阻膜更具有良好的耐化特性。 The main purpose of the present disclosure is to provide a polyimide positive photoresist composition, which can be cured at low temperature, and the obtained photoresist film has better chemical resistance properties.
本揭露的聚醯亞胺正型光阻組成物,包括:一樹脂成分;一交聯劑;一感光劑;以及一溶劑。其中,樹脂成分包括:81wt%至99wt%之聚醯亞胺樹脂;以及1wt%至19wt%之丙烯酸樹脂,包括一含環氧基的單體。 The disclosed polyimide positive photoresist composition includes: a resin component; a crosslinking agent; a photosensitive agent; and a solvent. Wherein, the resin component includes: 81wt% to 99wt% of polyimide resin; and 1wt% to 19wt% of acrylic resin, including an epoxy group-containing monomer.
於本揭露的組成物中,由於樹脂成分中的丙烯酸樹脂包括一含環氧基的單體,而可使聚醯亞胺正型光阻組成物得以在低溫固化。丙烯酸樹脂中的環氧基更可與聚醯亞胺樹脂交聯,而形成互穿網狀結構(Interpenetrating polymer network,IPN),提升固化後的聚合物的耐化性。此外,聚醯亞胺樹脂與交聯劑交聯,亦能提升固化後的聚合物的耐化性。同時,樹脂成分中包含特殊比例的聚醯亞胺樹脂及丙烯酸樹脂,可使聚醯亞胺正型光阻組成物即使在低溫固化後,所得的聚合物仍能具有良好的耐化特性。 In the composition of the present disclosure, since the acrylic resin in the resin component includes an epoxy group-containing monomer, the polyimide positive photoresist composition can be cured at low temperature. The epoxy group in the acrylic resin can be cross-linked with the polyimide resin to form an interpenetrating polymer network (IPN), which improves the chemical resistance of the cured polymer. In addition, the polyimide resin is cross-linked with a cross-linking agent, which can also improve the chemical resistance of the cured polymer. At the same time, the resin composition contains a special proportion of polyimide resin and acrylic resin, so that even after the polyimide positive photoresist composition is cured at low temperature, the resulting polymer still has good chemical resistance.
於本揭露的組成物中,以聚醯亞胺正型光阻組成物的總重量為基準,樹脂成分的含量可介於10wt%至70wt%之間,交聯劑的含量可介於1wt%至20wt%之間,感光劑的含量可介於0.05wt%至20wt%之間,而餘量為溶劑。 In the composition of the present disclosure, based on the total weight of the polyimide positive photoresist composition, the content of the resin component can be between 10wt% and 70wt%, and the content of the crosslinking agent can be between 1wt%. Between 0.05wt% and 20wt%, the content of photosensitizer can be between 0.05wt% and 20wt%, and the balance is solvent.
於本揭露的組成物中,以聚醯亞胺正型光阻組成物的總重量為基準,樹脂成分的含量可介於10wt%至70wt%之間。例如,樹脂成分的含量可介於20wt%至60wt%之間,介於30wt%至55wt%之間,或介於40wt%至50wt%之間。 In the composition of the present disclosure, based on the total weight of the polyimide positive photoresist composition, the content of the resin component can be between 10wt% and 70wt%. For example, the content of the resin component may be between 20wt% and 60wt%, between 30wt% and 55wt%, or between 40wt% and 50wt%.
於本揭露的組成物中,以聚醯亞胺正型光阻組成物的總重量為基準,交聯劑的含量可介於1wt%至20wt%之間。例如,交聯劑的含量可介於3wt%至15wt%之間,或介於4wt%至10wt%之間。 In the composition of the present disclosure, based on the total weight of the polyimide positive photoresist composition, the content of the crosslinking agent may be between 1 wt % and 20 wt %. For example, the content of the crosslinking agent may be between 3wt% and 15wt%, or between 4wt% and 10wt%.
於本揭露的組成物中,以聚醯亞胺正型光阻組成物的總重量為基準,感光劑的含量可介於0.05wt%至20wt%之間。例如,感光劑的含量可介於1wt%至15wt%之間,或介於5wt%至10wt%之間。 In the composition of the present disclosure, based on the total weight of the polyimide positive photoresist composition, the content of the photosensitive agent can be between 0.05wt% and 20wt%. For example, the content of the photosensitizer may be between 1 wt % and 15 wt %, or between 5 wt % and 10 wt %.
於本揭露的組成物中,聚醯亞胺樹脂可如下式(I)所示: In the composition of the present disclosure, the polyimide resin can be represented by the following formula (I):
其中,n為3至2,000之整數。 Wherein, n is an integer of 3 to 2,000.
於本揭露的組成物中,聚醯亞胺樹脂的分子量可介於3,000至20,000之間。例如,聚醯亞胺樹脂的分子量可介於3,000至10,000之間,介於5,000至10,000之間,或介於5,000至8,000之間。 In the composition of the present disclosure, the molecular weight of the polyimide resin can be between 3,000 and 20,000. For example, the polyimide resin may have a molecular weight between 3,000 and 10,000, between 5,000 and 10,000, or between 5,000 and 8,000.
於本揭露的組成物中,丙烯酸樹脂可包括一甲基丙烯酸(methacrylic acid)單體、一甲基丙烯酸縮水甘油酯(glycidyl methacrylate)單體及一甲基丙烯酸三環[5,2,1,02,6]癸-8-基酯(tricyclo[5,2,1,02,6]decane-8-ol methacrylate,TCDMA)單體;前述單體的化學式分別如下式(II-1)至(II-3)所示: In the composition of the present disclosure, the acrylic resin may include a methacrylic acid monomer, a glycidyl methacrylate monomer and a methacrylic tricyclo[5,2,1, 02,6]decane-8-yl ester (tricyclo[5,2,1,02,6]decane-8-ol methacrylate, TCDMA) monomer; the chemical formulas of the aforementioned monomers are as follows: (II-1) to ( II-3) as shown:
於本揭露組成物所包括的丙烯酸樹脂中,式(II-1)單體的含量可介於20mol%至50mol%之間,式(II-2)單體的含量可介於30mol%至60mol%之間,而式(II-3)單體的含量可介於10mol%至30mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-1) can be between 20 mol% and 50 mol%, and the content of the monomer of formula (II-2) can be between 30 mol% and 60 mol %, and the content of the monomer of formula (II-3) can be between 10mol% and 30mol%.
於本揭露的組成物中,丙烯酸樹脂可更包括一苯乙烯(styrene)單體,其化學式如下式(II-4)所示: In the composition of the present disclosure, the acrylic resin may further include a styrene monomer, the chemical formula of which is shown in the following formula (II-4):
於本揭露組成物所包括的丙烯酸樹脂中,式(II-1)單體的含量可介於20mol%至50mol%之間,式(II-2)單體的含量可介於30mol%至60mol%之間,式(II-3)單體的含量可介於10mol%至30mol%之間,而式(II-4)單體的含量可介於0.1mol%至10mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-1) can be between 20 mol% and 50 mol%, and the content of the monomer of formula (II-2) can be between 30 mol% and 60 mol %, the content of the monomer of formula (II-3) can be between 10 mol% and 30 mol%, and the content of the monomer of formula (II-4) can be between 0.1 mol% and 10 mol%.
於本揭露組成物所包括的丙烯酸樹脂中,式(II-1)單體的含量可介於20mol%至50mol%之間。例如,式(II-1)單體的含量可介於25mol%至40mol%之間,或介於30mol%至35mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-1) may be between 20 mol% and 50 mol%. For example, the content of the monomer of formula (II-1) may be between 25 mol% and 40 mol%, or between 30 mol% and 35 mol%.
於本揭露組成物所包括的丙烯酸樹脂中,式(II-2)單體的含量可介於30mol%至60mol%之間。例如,式(II-2)單體的含量可介於35mol%至50mol%之間,或介於40mol%至45mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-2) can be between 30 mol% and 60 mol%. For example, the content of the monomer of formula (II-2) may be between 35 mol% and 50 mol%, or between 40 mol% and 45 mol%.
於本揭露組成物所包括的丙烯酸樹脂中,式(II-3)單體的含量可介於10mol%至30mol%之間。例如,式(II-3)單體的含量可介於15mol%至25mol%之間,或介於18mol%至22mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-3) can be between 10 mol% and 30 mol%. For example, the content of the monomer of formula (II-3) may be between 15 mol% and 25 mol%, or between 18 mol% and 22 mol%.
於本揭露組成物所包括的丙烯酸樹脂中,式(II-4)單體的含量可介於0.1mol%至10mol%之間。例如,式(II-4)單體的含量可介於1mol%至7mol%之間,或介於3mol%至5mol%之間。 In the acrylic resin included in the disclosed composition, the content of the monomer of formula (II-4) may be between 0.1 mol% and 10 mol%. For example, the content of the monomer of formula (II-4) may be between 1 mol% and 7 mol%, or between 3 mol% and 5 mol%.
於本揭露的組成物中,丙烯酸樹脂的分子量可介於5,000至20,000之間。例如,丙烯酸樹脂的分子量可介於6,000至17,000之間,介於8,000至14,000之間,或介於9,000至11,000之間。 In the composition of the present disclosure, the molecular weight of the acrylic resin can be between 5,000 and 20,000. For example, the molecular weight of the acrylic resin may be between 6,000 and 17,000, between 8,000 and 14,000, or between 9,000 and 11,000.
於本揭露的組成物中,感光劑的種類並無特殊限制,只要為藉由活性放射線而曝光時能產生酸的化合物即可。其中,感光劑為一醌二疊氮化合 物。其中,醌二疊氮化合物可列舉公知的1,2-醌二疊氮-4-磺酸酯(1,2-quinonediazide-4-sulfonic acid ester)化合物、1,2-醌二疊氮-5-磺酸酯(1,2-quinonediazide-5-sulfonic acid ester)化合物、1,2-醌二疊氮-6-磺酸酯(1,2-quinonediazide-6-sulfonic acid ester)化合物、1,2-醌二疊氮-7-磺酸酯(1,2-quinonediazide-7-sulfonic acid ester)化合物、1,2-醌二疊氮-8-磺酸酯(1,2-quinonediazide-8-sulfonicacid ester)化合物。具體可列舉:三羥基二苯甲酮(trihydroxy benzophenone)的1,2-萘醌二疊氮磺酸酯類、四羥基二苯甲酮(tetrahydroxy benzophenone)的1,2-萘醌二疊氮磺酸酯類、五羥基二苯甲酮(pentahydroxy benzophenone)的1,2-萘醌二疊氮磺酸酯類、六羥基二苯甲酮(hexahydroxy benzophenone)的1,2-萘醌二疊氮磺酸酯類、(多羥基)烷烴((polyhydroxy)alkane)的1,2-萘醌二疊氮磺酸酯類等。於本揭露中,醌二疊氮化合物的具體例子可如下式(III)所示: In the composition of the present disclosure, the type of the photosensitive agent is not particularly limited, as long as it is a compound that can generate acid when exposed to actinic radiation. Among them, the photosensitizer is a quinone diazide compound thing. Among them, the quinonediazide compound includes known 1,2-quinonediazide-4-sulfonic acid ester (1,2-quinonediazide-4-sulfonic acid ester) compound, 1,2-quinonediazide-5 -sulfonic acid ester (1,2-quinonediazide-5-sulfonic acid ester) compound, 1,2-quinonediazide-6-sulfonic acid ester (1,2-quinonediazide-6-sulfonic acid ester) compound, 1, 2-quinonediazide-7-sulfonic acid ester (1,2-quinonediazide-7-sulfonic acid ester) compound, 1,2-quinonediazide-8-sulfonic acid ester (1,2-quinonediazide-8- sulfonic acid ester) compound. Specifically, 1,2-naphthoquinone diazide sulfonates of trihydroxy benzophenone, 1,2-naphthoquinone diazide sulfonate of tetrahydroxy benzophenone Esters, 1,2-naphthoquinone diazide sulfonate of pentahydroxy benzophenone, 1,2-naphthoquinone diazide sulfonate of hexahydroxy benzophenone Esters, 1,2-naphthoquinone diazide sulfonates of (polyhydroxy)alkane, etc. In the present disclosure, specific examples of quinonediazide compounds can be shown in the following formula (III):
於本揭露的組成物中,溶劑的種類並無特殊限制,只要組成物中的成分可溶於其中即可。其中,溶劑的具體例子包括,但不限於,乙酸丙二醇單甲基醚酯(Propylene Glycol Monomethyl Ether Acetate)、丙二醇甲基醚 (Propylene Glycol Monomethyl Ether)、乳酸酯類(例如:乳酸乙酯(Ethyl Lactate)、乳酸甲酯)、丙二醇單烷基醚類(例如:丙二醇單乙基醚、丙二醇單丙基醚)、酮類(例如:環己酮)、或內酯類(例如:γ-丁內酯)。上述溶劑可單獨使用或兩種或以上混合使用,而無特殊限制。於本揭露的實施例中,溶劑為乳酸乙酯。 In the composition of the present disclosure, the type of solvent is not particularly limited, as long as the components in the composition are soluble therein. Wherein, specific examples of solvents include, but are not limited to, propylene glycol monomethyl ether acetate (Propylene Glycol Monomethyl Ether Acetate), propylene glycol methyl ether (Propylene Glycol Monomethyl Ether), lactic acid esters (such as: ethyl lactate (Ethyl Lactate), methyl lactate), propylene glycol monoalkyl ethers (such as: propylene glycol monoethyl ether, propylene glycol monopropyl ether), ketones (for example: cyclohexanone), or lactones (for example: γ-butyrolactone). The above solvents may be used alone or in combination of two or more without particular limitation. In the embodiments of the present disclosure, the solvent is ethyl lactate.
於本揭露的組成物中,交聯劑的種類並無特殊限制,只要是因酸引發光阻組成物進行交聯反應即可。交聯劑可為一三聚氰胺類交聯劑。其中,三聚氰胺類交聯劑可包括至少四個-OCH3,例如包括六個-OCH3。於本揭露中,三聚氰胺類交聯劑的具體例子可為2,4,6-三[二(甲氧基甲基)胺基]-1,3,5-三嗪(2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine)或(N-(4-(二(甲氧基甲基)胺基)-6-(甲氧基甲基)胺基-1,3,5-三嗪-2-基)-N-(甲氧基甲基)氨基)甲醇(N-(4-(bis(methoxymethyl)amino)-6-(methoxymethyl)amino-1,3,5-triazin-2-yl)-N-(methoxymethyl)amino)methanol),其化學式分別如下式(IV-1)及(IV-2)所示。 In the composition of the present disclosure, the type of the cross-linking agent is not particularly limited, as long as the cross-linking reaction of the photoresist composition is triggered by acid. The crosslinking agent can be a melamine crosslinking agent. Wherein, the melamine-based crosslinking agent may include at least four -OCH 3 , for example, six -OCH 3 . In the present disclosure, a specific example of a melamine-based crosslinking agent may be 2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine (2,4,6- tris[bis(methoxymethyl)amino]-1,3,5-triazine) or (N-(4-(di(methoxymethyl)amino)-6-(methoxymethyl)amino-1 ,3,5-Triazin-2-yl)-N-(methoxymethyl)amino)methanol (N-(4-(bis(methoxymethyl)amino)-6-(methoxymethyl)amino-1,3, 5-triazin-2-yl)-N-(methoxymethyl)amino)methanol), the chemical formulas of which are shown in the following formulas (IV-1) and (IV-2) respectively.
本揭露的組成物可用於低溫固化的顯影製程上。其中,低溫可為250℃以下,例如:180℃至230℃。 The composition of the present disclosure can be used in a low-temperature curing development process. Wherein, the low temperature may be below 250°C, for example: 180°C to 230°C.
以下係藉由具體實施例說明本揭露之實施方式,熟習此技藝之人士可由本說明書所揭示之內容輕易地了解本揭露之其他優點與功效。本揭露亦可藉由其他不同的具體實施例加以施行或應用,本說明書中的各項細節亦可針對不同觀點與應用,在不悖離本創作之精神下進行各種修飾與變更。 The implementation of the present disclosure is described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present disclosure from the content disclosed in this specification. This disclosure can also be implemented or applied by other different specific embodiments, and various modifications and changes can be made to the details in this specification for different viewpoints and applications without departing from the spirit of this creation.
除非文中另有說明,否則說明書及所附申請專利範圍中所使用之單數形式「一」及「該」包括一或複數個體。 As used in the specification and the appended claims, the singular forms "a" and "the" include one or plural individuals unless the context dictates otherwise.
除非文中另有說明,否則說明書及所附申請專利範圍中所使用之術語「或」通常包括「及/或」之含義。 Unless otherwise stated in the context, the term "or" used in the specification and appended claims generally includes the meaning of "and/or".
本揭露將藉由實施例更具體地說明,但該等實施例並非用於限制本揭露之範疇。除非特別指明,於下列製備例、實施例與比較例中,溫度為攝氏溫度,份數及百分比係以重量計。重量份數和體積份數之關係就如同公斤和公升之關係。 The present disclosure will be described more specifically through examples, but these examples are not intended to limit the scope of the present disclosure. Unless otherwise specified, in the following preparation examples, examples and comparative examples, the temperature is in degrees centigrade, and the parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters.
聚醯亞胺樹脂的合成 Synthesis of Polyimide Resin
於乾燥氮氣流下,將2,2-雙(3-氨基-4-羥基苯基)六氟丙烷(以下稱為APAF)91.6重量份與4,4'-氧雙鄰苯二甲酸酐(以下稱為ODPA)62.0重量份溶解於二乙二醇甲基乙基醚(Methyl Ethyl Di Glycol,MEDG)367.6重量份,於60℃下反應2小時,於反應中添加作為封端劑的六氫苯酐(以下稱為HHPA)129.5重量份,繼而於60℃下攪拌4小時。將1-乙基-吡啶(1-ethyl pyridine)0.34g重量份加入反應中,其後於180℃下攪拌4小時。攪拌結束後,將溶液投入至水3L中,進行過濾而回收沈澱,利用水清洗3次後,使用真空乾燥機於80℃下進行20小時乾燥。對所得的聚合物固體測定紅外吸收光譜,結果於1780cm-1附近、1377cm-1附近檢測到由聚醯亞胺引起的醯亞胺結構的吸收峰,其分子量約3000-20000克/莫耳。 Under dry nitrogen flow, 91.6 parts by weight of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as APAF) and 4,4'-oxydiphthalic anhydride (hereinafter referred to as 62.0 parts by weight of ODPA) were dissolved in 367.6 parts by weight of diethylene glycol methyl ethyl ether (Methyl Ethyl Di Glycol, MEDG), reacted at 60°C for 2 hours, and added hexahydrophthalic anhydride ( Hereinafter, it is referred to as HHPA) 129.5 weight part, and it stirred at 60 degreeC for 4 hours further. 0.34 g parts by weight of 1-ethylpyridine was added to the reaction, followed by stirring at 180° C. for 4 hours. After completion of the stirring, the solution was poured into 3 L of water, and the precipitate was collected by filtration, washed three times with water, and then dried at 80° C. for 20 hours using a vacuum dryer. The infrared absorption spectrum of the obtained polymer solid was measured, and the absorption peaks of the imide structure caused by polyimide were detected around 1780cm- 1 and 1377cm -1 , and its molecular weight was about 3000-20000 g/mol.
丙烯酸樹脂的合成 Synthesis of Acrylic Resin
在裝有冷凝管、攪拌機的燒瓶中,投入4重量份熱自由基起始劑2,2’-偶氮雙異丁基(AIBN)、282重量份的溶劑二乙二醇甲基乙基醚(Methyl Ethyl Di Glycol,MEDG),接著投入33重量份甲基丙烯酸三環[5,2,1,02,6]癸-8-基酯(TCDMA)、21重量份的甲基丙烯酸(MAA)、3重量份苯乙烯(Styrene)、45.5重量份甲基丙烯酸縮水甘油酯(GMA),用氮氣置換後,開始快速攪拌,使溫度維持在65℃下3個半小時,接著升溫到75℃下2個半小時,得到一丙烯酸樹脂,其分子量約8000-14000克/莫耳。 In a flask equipped with a condenser tube and a stirrer, put 4 parts by weight of thermal radical initiator 2,2'-azobisisobutyl (AIBN), 282 parts by weight of solvent diethylene glycol methyl ethyl ether (Methyl Ethyl Di Glycol, MEDG), followed by adding 33 parts by weight of tricyclo[5,2,1,02,6]dec-8-yl methacrylate (TCDMA), 21 parts by weight of methacrylic acid (MAA) , 3 parts by weight of styrene (Styrene), 45.5 parts by weight of glycidyl methacrylate (GMA), after replacing with nitrogen, start rapid stirring, keep the temperature at 65°C for 3 and a half hours, then heat up to 75°C After 2.5 hours, an acrylic resin with a molecular weight of about 8000-14000 g/mol was obtained.
聚醯亞胺正型光阻組成物 Polyimide positive photoresist composition
將前述所製備的聚醯亞胺樹脂及丙烯酸樹脂,與交聯劑、感光劑及溶劑依照表1所示之組成配方配製成實施例1至4及比較例1至2之聚醯亞胺正型光阻組成物。 The above-prepared polyimide resin and acrylic resin, and crosslinking agent, photosensitive agent and solvent are formulated into the polyimides of Examples 1 to 4 and Comparative Examples 1 to 2 according to the composition formula shown in Table 1 Positive photoresist composition.
光阻膜製備 Photoresist film preparation
於光阻旋轉塗佈前,在6英吋的矽晶圓上進行HMDS蒸氣塗佈,將實施例1至4及比較例1至2的光阻組成物塗佈於6吋矽晶圓上,而後於120℃下預烘烤120秒,得到厚度為3μm的光阻層。將光阻層以Ultratech 1500 stepper(Boardband;NA=0.24)進行曝光;於23℃下以2.38% TMAH進行顯影60秒,並以去離子水清洗30秒,並進行烘烤製程於氮氣下(氧濃度為50ppm以下),50℃升溫至110℃(升溫速率3.5℃/min),持溫30分鐘;再升溫至180℃(升溫速率3.5℃/min),持溫60分鐘,緩慢降溫達到50℃或更低時。最後,評估曝光顯影後光阻層的光阻圖案。 Before photoresist spin coating, HMDS vapor coating was carried out on a 6-inch silicon wafer, and the photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 2 were coated on a 6-inch silicon wafer, Then pre-baking at 120° C. for 120 seconds to obtain a photoresist layer with a thickness of 3 μm. The photoresist layer was exposed with Ultratech 1500 stepper (Boardband; NA=0.24); developed at 23°C with 2.38% TMAH for 60 seconds, and cleaned with deionized water for 30 seconds, and baked under nitrogen (oxygen Concentration below 50ppm), heat up from 50°C to 110°C (heating rate 3.5°C/min), hold temperature for 30 minutes; then heat up to 180°C (heating rate 3.5°C/min), hold temperature for 60 minutes, slowly cool down to 50°C or lower. Finally, evaluate the photoresist pattern of the photoresist layer after exposure and development.
耐化學性測試 Chemical Resistance Test
固化膜的耐化學性的評估方法簡述如下。於光阻旋轉塗佈前,在6英吋的矽晶圓上進行HMDS蒸氣塗佈,將實施例1至4及比較例1至2的光阻組成物塗佈於6吋矽晶圓上,而後於120℃下預烘烤120秒,得到厚度為3μm的光阻 層。將光阻層以Ultratech 1500 stepper(Boardband;NA=0.24)進行曝光;於23℃下以2.38% TMAH進行顯影60秒,並以去離子水清洗30秒,並進行烘烤製程於氮氣下(氧濃度為50ppm以下),50℃升溫至110℃(升溫速率3.5℃/min),持溫30分鐘;再升溫至180℃(升溫速率3.5℃/min),持溫60分鐘,緩慢降溫達到50℃或更低時,取出晶片,並且在測量膜厚度之後,將晶片置於N-甲基吡咯烷酮(N-methyl-pyrrolidinone,NMP)光阻剝離劑的溶劑中於80℃下60分鐘。從溶劑中取出的晶片用純水洗滌後,再次測量膜厚。如果變化率的絕對值超過10%或圖型脫落,則不足(NG),在10%以內並圖形狀況良好,則表示是好(OK)。 The evaluation method of the chemical resistance of the cured film is briefly described below. Before photoresist spin coating, HMDS vapor coating was carried out on a 6-inch silicon wafer, and the photoresist compositions of Examples 1 to 4 and Comparative Examples 1 to 2 were coated on a 6-inch silicon wafer, Then pre-baked at 120°C for 120 seconds to obtain a photoresist with a thickness of 3 μm Floor. The photoresist layer was exposed with Ultratech 1500 stepper (Boardband; NA=0.24); developed at 23°C with 2.38% TMAH for 60 seconds, and cleaned with deionized water for 30 seconds, and baked under nitrogen (oxygen Concentration below 50ppm), heat up from 50°C to 110°C (heating rate 3.5°C/min), hold temperature for 30 minutes; then heat up to 180°C (heating rate 3.5°C/min), hold temperature for 60 minutes, slowly cool down to 50°C or lower, the wafer was taken out, and after measuring the film thickness, the wafer was placed in a solvent of N-methyl-pyrrolidinone (NMP) photoresist stripper at 80° C. for 60 minutes. After the wafer removed from the solvent was washed with pure water, the film thickness was measured again. If the absolute value of the rate of change exceeds 10% or the pattern falls off, it is insufficient (NG), and if it is within 10% and the pattern is in good condition, it is good (OK).
表1
表1中的感光劑之5-萘醌二疊氮磺酸酯類感光劑如下式(III)所示,其商品名為TPPA-250。 The 5-naphthoquinone diazide sulfonate photosensitizer in Table 1 is represented by the following formula (III), and its trade name is TPPA-250.
表1中的交聯劑之三聚氰胺化合物如下式(IV-1)所示,其商品名為NIKALAC MW-390。 The melamine compound of the crosslinking agent in Table 1 is represented by the following formula (IV-1), and its trade name is NIKALAC MW-390.
如實施例1至4及比較例1至2的結果顯示,當樹脂成分中未使用丙烯酸樹脂時,對於NMP光阻剝離劑的耐化特性測試效果不佳;而當樹脂成分中含有特定比例的丙烯酸樹脂時,固化後的光阻膜對NMP光阻剝離劑可展現良好的耐化特性。特別是,由實施例1至4的結果顯示,當樹脂成分中添加適量的丙烯酸樹脂時,固化後的光阻膜對NMP光阻剝離劑可展現良好的耐化特性;然而,由比較例2的結果顯示,當樹脂成分中所添加的丙烯酸樹脂過量時,固化後的光阻膜對NMP光阻剝離劑的耐化特性不佳。 As the results of Examples 1 to 4 and Comparative Examples 1 to 2 show, when no acrylic resin is used in the resin component, the chemical resistance test effect of the NMP photoresist stripping agent is not good; and when the resin component contains a specific proportion of When using acrylic resin, the cured photoresist film can show good chemical resistance to NMP photoresist stripper. In particular, the results of Examples 1 to 4 show that when an appropriate amount of acrylic resin is added to the resin component, the cured photoresist film can exhibit good chemical resistance to NMP photoresist strippers; however, from Comparative Example 2 The results show that when the acrylic resin added in the resin component is excessive, the chemical resistance of the cured photoresist film to the NMP photoresist stripper is not good.
此外,實施例1至實施例4之光阻組成物,經曝光顯影後所得到的光阻膜,光阻圖案的解析度可高達2μm,且更具有良好的耐化特性。 In addition, for the photoresist compositions of Examples 1 to 4, the photoresist film obtained after exposure and development can have a photoresist pattern resolution as high as 2 μm, and has better chemical resistance.
綜上所述,以本揭露的聚醯亞胺正型光阻組成物所形成的光阻膜具有良好的耐化特性。因此,當於以本揭露的組成物所形成的光阻膜上形成金 屬圖案(例如:電極、線路或其他)時,因光阻膜具有良好的耐化特性,故形成金屬圖案時所使用鹼性的光阻剝離劑不會破壞光阻膜圖案,使得所製得的電子產品具有高良率及長使用壽命。 In summary, the photoresist film formed with the polyimide positive photoresist composition of the present disclosure has good chemical resistance. Therefore, when gold is formed on the photoresist film formed with the composition of the present disclosure When it is a pattern (such as: electrode, line or others), because the photoresist film has good chemical resistance, the alkaline photoresist stripper used when forming the metal pattern will not destroy the photoresist film pattern, so that the obtained High-quality electronic products have high yield and long service life.
上述實施例僅係為了方便說明而舉例而已,本揭露所主張之權利範圍自應以申請專利範圍所述為準,而非僅限於上述實施例。 The above-mentioned embodiments are only examples for the convenience of description, and the scope of rights claimed in the present disclosure should be based on the scope of the patent application, rather than limited to the above-mentioned embodiments.
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