TWI580724B - Composition for etching mask and pattern forming method - Google Patents
Composition for etching mask and pattern forming method Download PDFInfo
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- TWI580724B TWI580724B TW101143091A TW101143091A TWI580724B TW I580724 B TWI580724 B TW I580724B TW 101143091 A TW101143091 A TW 101143091A TW 101143091 A TW101143091 A TW 101143091A TW I580724 B TWI580724 B TW I580724B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description
本發明係關於蝕刻太陽能電池用基板時作為遮蔽劑使用之蝕刻遮罩用組成物。 The present invention relates to a composition for an etching mask used as a shielding agent when etching a substrate for a solar cell.
太陽能電池之製造步驟中，在部分蝕刻處理基板時使用遮蔽劑。過去，該步驟中雖使用光阻，但現今為減少步驟數而檢討印刷型阻劑之應用。蝕刻處理太陽能電池用基板時之蝕刻液則使用氫氟酸、硝酸等強酸。因此，作為對印刷型阻劑所要求之特性，要求有於蝕刻時對蝕刻液之耐酸性，且可藉印刷法形成圖型。 In the manufacturing step of the solar cell, a masking agent is used when partially etching the substrate. In the past, although photoresist was used in this step, the application of the printed resist was reviewed to reduce the number of steps. A strong acid such as hydrofluoric acid or nitric acid is used as the etching solution for etching the substrate for a solar cell. Therefore, as a characteristic required for a printing type resist, acid resistance to an etching liquid at the time of etching is required, and a pattern can be formed by a printing method.
[專利文獻1]日本特開平9-293888號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-293888
光阻所使用之丙烯酸樹脂在耐酸性方面不足，難以作為太陽能電池基板蝕刻用之遮蔽劑使用。且，使用於光阻中使用之低沸點溶劑製作之油墨由於印刷之安定性不足，故難以形成良好之圖型。 The acrylic resin used for the photoresist is insufficient in acid resistance, and it is difficult to use it as a shielding agent for etching a solar cell substrate. Further, since the ink produced by using the low boiling point solvent used in the photoresist is insufficient in stability of printing, it is difficult to form a good pattern.
本發明係鑑於該等課題而完成者，其目的係提供一種可提高將蝕刻遮罩用組成物印刷於太陽能電池用基板上時之耐酸性及印刷安定性之技術。 The present invention has been made in view of the above problems, and an object thereof is to provide a technique for improving acid resistance and printing stability when a composition for an etching mask is printed on a substrate for a solar cell.
本發明之一樣態為蝕刻遮罩用組成物。該蝕刻遮罩用組成物之特徵為含有酚醛清漆樹脂(A)，及沸點為190℃以上之溶劑(B)，其中前述溶劑(B)之含量相對於溶劑全體為70質量%以上，且該組成物為非感光性。 The same state of the present invention is a composition for etching a mask. The composition for the etching mask is characterized by containing a novolak resin (A) and a solvent (B) having a boiling point of 190 ° C or higher, wherein the content of the solvent (B) is 70% by mass or more based on the total amount of the solvent, and The composition is non-photosensitive.
依據上述樣態之蝕刻遮罩用組成物，可提高印刷於太陽能電池用基板時之耐酸性及印刷安定性。 According to the composition for etching the mask described above, the acid resistance and the printing stability when printed on the substrate for a solar cell can be improved.
上述樣態之蝕刻遮罩用組成物中，亦可進而具備矽系、丙烯酸系或氟系之界面活性劑(C)。 Further, the composition for etching the mask described above may further contain a lanthanide, acrylic or fluorine-based surfactant (C).
本發明之另一樣態為圖型形成方法。該圖型形成方法包含於基板上使用如上述任一樣態之太陽能電池用基板之蝕刻遮罩用組成物，以印刷法形成遮罩圖型之步驟，烘烤遮罩圖型之步驟，蝕刻基板而轉印遮罩圖型之步驟，及去除遮罩圖型之步驟。 Another aspect of the invention is a pattern forming method. The pattern forming method includes the step of forming a mask pattern by a printing method using a composition for etching a mask of a substrate for a solar cell according to any of the above-described states, and baking the substrate pattern by a step of baking a mask pattern. And the steps of transferring the mask pattern and removing the mask pattern.
本發明將參考較佳具體例加以敘述。但此僅係舉例說明本發明，並不用於限制本發明之範圍。 The invention will now be described with reference to preferred embodiments. However, this is merely illustrative of the invention and is not intended to limit the scope of the invention.
實施形態之蝕刻遮罩用組成物為非感光性，且適用作為部分蝕刻處理太陽能電池用基板時使用之蝕刻遮罩。 The composition for an etching mask of the embodiment is non-photosensitive, and is suitable as an etching mask used for partially etching a substrate for a solar cell.
實施形態之蝕刻遮罩用組成物包含酚醛清漆樹脂(A)及沸點為190℃以上之溶劑(B)。 The composition for an etching mask of the embodiment contains a novolak resin (A) and a solvent (B) having a boiling point of 190 ° C or higher.
酚醛清漆樹脂(A)列舉為在鹽酸、硫酸、甲酸、草酸、對甲苯磺酸等酸性觸媒下，使下述例示之酚類，與下述例示之醛類反應獲得之酚醛清漆樹脂等。 The novolac resin (A) is a novolac resin obtained by reacting the phenols exemplified below with an aldehyde exemplified below under an acidic catalyst such as hydrochloric acid, sulfuric acid, formic acid, oxalic acid or p-toluenesulfonic acid.
酚類列舉為例如苯酚；間-甲酚、對-甲酚、鄰-甲酚等甲酚類；2,3-二甲酚、2,5-二甲酚、3,5-二甲酚、3,4-二甲酚等二甲酚類；間-乙基酚、對-乙基酚、鄰-乙基酚、2,3,5-三甲基酚、2,3,5-三乙基酚、4-第三丁基酚、3-第三丁基酚、2-第三丁基酚、2-第三丁基-4-甲基酚、2-第三丁基-5-甲基酚等烷基酚類；對-甲氧基酚、間-甲氧基酚、對-乙氧基酚、間-乙氧基酚、對-丙氧基酚、間-丙氧基酚等烷氧基酚類；鄰-異丙烯基酚、對-異丙烯基酚、2-甲基-4-異丙烯基酚、2-乙基-4-異丙烯基酚等異丙烯基酚類；苯基酚等芳基酚類；4,4’-二羥基聯苯、雙酚A、間苯二酚、氫醌、聯苯三酚等多羥基酚類等。該等可單獨使用，且亦可組合兩種以上使用。該等酚類中，最好為間-甲酚、對-甲酚。 Phenols are exemplified by, for example, phenol; cresols such as m-cresol, p-cresol, o-cresol, etc.; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, Dimethyl phenols such as 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethyl Phenol, 4-tert-butyl phenol, 3-tert-butyl phenol, 2-tert-butyl phenol, 2-tert-butyl-4-methyl phenol, 2-tert-butyl-5- Alkylphenols such as phenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, etc. Alkoxyphenols; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol; An aryl phenol such as phenylphenol; a polyhydric phenol such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcin, hydroquinone or biphenyltriol. These may be used alone or in combination of two or more. Among these phenols, m-cresol and p-cresol are preferred.
醛類列舉為例如甲醛、仲甲醛、三噁烷、乙醛、丙醛、丁醛、三甲基乙醛、丙烯醛、巴豆醛、環己醛、糠醛、呋喃丙烯醛、苯甲醛、對苯二甲醛、苯基乙醛、α-苯基丙醛、β-苯基丙醛、鄰-羥基苯甲醛、間-羥基苯甲醛、對-羥基苯甲醛、鄰-甲基苯甲醛、間-甲基苯甲醛、對-甲基苯甲醛、鄰-氯苯甲醛、間-氯苯甲醛、對-氯苯甲醛、桂皮醛等。該等可單獨使用亦可組合兩種以上使用。該等醛類中，就取得容易而言較好為甲醛。 The aldehydes are listed, for example, as formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanal, furfural, furan acrolein, benzaldehyde, para-benzene. Diformaldehyde, phenylacetaldehyde, α-phenylpropanal, β-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-A Benzobenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, and the like. These may be used alone or in combination of two or more. Among these aldehydes, formaldehyde is preferred because it is easy to obtain.
酚醛清漆樹脂(A)可由一種酚醛清漆樹脂組成，亦可由兩種以上之酚醛清漆樹脂組成。酚醛清漆樹脂(A)由兩種以上之酚醛清漆樹脂組成時，各酚醛清漆樹脂之 Mw並無特別限制，但較好以使酚醛清漆樹脂(A)全體之Mw成為1000~100000之方式調製。尤其使用噴墨印刷法時，較好使(A)全體之Mw成為1000~3000之方式調製。又，酚醛清漆樹脂(A)在蝕刻遮罩用組成物中較好包含30~70質量%。使用噴墨印刷法時，蝕刻遮罩用組成物中較好包含10~30質量%。又，酚醛清漆樹脂(A)在蝕刻遮罩用組成物中之固體成分中較好為90質量%以上，更好為95質量%以上，最好為98質量%以上。 The novolak resin (A) may be composed of a novolac resin or may be composed of two or more novolak resins. When the novolac resin (A) is composed of two or more novolak resins, each novolac resin Mw is not particularly limited, but it is preferably prepared so that the Mw of the entire novolac resin (A) is from 1,000 to 100,000. In particular, when the inkjet printing method is used, it is preferred to prepare the (M) overall Mw to be 1000 to 3000. Further, the novolak resin (A) preferably contains 30 to 70% by mass of the composition for etching the mask. When the inkjet printing method is used, the composition for etching the mask preferably contains 10 to 30% by mass. Further, the novolac resin (A) is preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 98% by mass or more, based on the solid content of the composition for etching the mask.
以上說明之酚醛清漆樹脂(A)之共通特性舉例為耐酸性優異。 The common characteristics of the novolac resin (A) described above are exemplified by excellent acid resistance.
溶劑(B)之具體例列舉為乙二醇、己二醇、丙二醇二乙酸酯、1,3-丁二醇二乙酸酯、二乙二醇、二丙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丙基醚、二乙二醇單丁基醚、二乙二醇單苯基醚、二乙二醇二乙基醚、二丙二醇單甲基醚、三丙二醇單甲基醚、乙二醇單丁基醚乙酸酯、乙二醇單苯基醚乙酸酯、二乙二醇單甲基醚乙酸酯、二乙二醇單乙基醚乙酸酯、二乙二醇單丙基醚乙酸酯、二乙二醇單苯基醚乙酸酯、二丙二醇單甲基醚乙酸酯、二乙二醇單丁基醚乙酸酯、丙三醇、苄基醇、乙酸3-甲基-3-甲氧基丁酯、乙酸3-乙基-3-甲氧基丁酯、乙酸2-甲氧基戊酯、乙酸3-甲氧基戊酯、乙酸4-甲氧基戊酯、乙酸2-甲基-3-甲氧基戊酯、乙酸3-甲基-3-甲氧基戊酯、乙酸3-甲基-4-甲氧基戊酯、乙酸4-甲基-4-甲氧基戊酯、二己基醚、乙酸苄酯、苯甲酸乙酯、馬來酸二乙酯、 γ-丁內酯、帖烯醇等。該等可單獨使用，亦可組合兩種以上使用。 Specific examples of the solvent (B) are ethylene glycol, hexanediol, propylene glycol diacetate, 1,3-butylene glycol diacetate, diethylene glycol, dipropylene glycol, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, diethylene glycol diethyl ether, dipropylene glycol single Methyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol single Ethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether Acid ester, glycerol, benzyl alcohol, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-methoxypentyl acetate, acetic acid 3 -Methoxyamyl ester, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl acetate- 4-methoxypentyl ester, 4-methyl-4-methoxypentyl acetate, dihexyl ether, benzyl acetate, ethyl benzoate, Malay Diethyl acid, Γ-butyrolactone, ene alcohol, and the like. These may be used singly or in combination of two or more.
實施形態之蝕刻遮罩用組成物亦包含上述溶劑(B)以外之溶劑。但，相對於溶劑全體之溶劑(B)含量為70質量%以上，較好為90質量%以上。 The composition for an etching mask of the embodiment also contains a solvent other than the above solvent (B). However, the solvent (B) content based on the entire solvent is 70% by mass or more, preferably 90% by mass or more.
至於溶劑(B)以外之溶劑(沸點未達180℃之溶劑(B’))列舉為環己酮、甲基-正戊基酮、甲基異戊基酮、2-庚酮等酮類；乙二醇、丙二醇等多元醇類；丙二醇單甲基醚乙酸酯(PGMEA)、丙二醇單甲基醚(PGME)、二丙二醇二甲基醚、丙二醇丙基醚等多元醇類之衍生物；其他之乙酸丁酯、乙醯基乙酸乙酯、乳酸丁酯、草酸二乙酯等酯類。該等中，以丙二醇單甲基醚乙酸酯、2-庚酮、乙酸丁酯較佳。含溶劑(B’)時，相對於溶劑全體之溶劑(B’)含量為1~30質量%，較好為1~20質量%。 The solvent other than the solvent (B) (the solvent (B') having a boiling point of less than 180 ° C) is exemplified by a ketone such as cyclohexanone, methyl-n-pentyl ketone, methyl isoamyl ketone or 2-heptanone; Polyols such as ethylene glycol and propylene glycol; derivatives of polyhydric alcohols such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), dipropylene glycol dimethyl ether, and propylene glycol propyl ether; Other esters such as butyl acetate, ethyl acetoxyacetate, butyl lactate, and diethyl oxalate. Among these, propylene glycol monomethyl ether acetate, 2-heptanone, and butyl acetate are preferred. When the solvent (B') is contained, the solvent (B') content based on the entire solvent is from 1 to 30% by mass, preferably from 1 to 20% by mass.
實施形態之蝕刻遮罩用組成物亦可進而具備氟系、矽系或丙烯酸系之界面活性劑(C)。 The etch mask composition of the embodiment may further contain a fluorine-based, lanthanide- or acrylic-based surfactant (C).
氟系界面活性劑(C)列舉為KL-600(共榮社化學製造)、APX-4082B(共榮社化學製造)等。矽系界面活性劑(C)列舉為以聚酯改質之聚二甲基矽氧烷為主成分之BYK-310(BYK化學製造)、以芳烷基改質之聚甲基烷基矽氧烷作為主成分之BYK-323(BYK化學製造)、以聚醚改質之含有羥基之聚二甲基矽氧烷作為主成分之BYK-SILCLEAN3720(BYK化學製造)、以聚醚改質之甲基聚 矽氧烷作為主成分之KF-353(信越化學工業(股)製造)等。另外，丙烯酸系界面活性劑(C)列舉為BYK-354(BYK化學製造)。該等中，以氟系或矽系之界面活性劑較佳，矽系之界面活性劑中以聚二甲基矽氧烷系之界面活性劑較佳。界面活性劑(C)之添加量較好為0.001質量%~1.0質量%，更好為0.01質量%~0.1質量%。 The fluorine-based surfactant (C) is exemplified by KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and APX-4082B (manufactured by Kyoeisha Chemical Co., Ltd.). The lanthanide surfactant (C) is exemplified by BYK-310 (BYK Chemical Co., Ltd.) which is mainly composed of polyester modified polydimethyl siloxane, and polymethylalkyl oxime modified by aralkyl group. BYK-323 (manufactured by BYK Chemical Co., Ltd.) with alkane as a main component, BYK-SILCLEAN 3720 (BYK Chemical Co., Ltd.) with a polyether-modified polydimethyl methoxy alkane having a hydroxyl group as a main component, and a modified polyether Foundation KF-353 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like as a main component. Further, the acrylic surfactant (C) is exemplified by BYK-354 (manufactured by BYK Chemical Co., Ltd.). Among these, a fluorine- or quinone-based surfactant is preferred, and a dimethyl siloxane-based surfactant is preferred among the quinone-based surfactants. The amount of the surfactant (C) to be added is preferably from 0.001% by mass to 1.0% by mass, more preferably from 0.01% by mass to 0.1% by mass.
以上說明之蝕刻遮罩用組成物藉由包含耐酸性優異之酚醛清漆樹脂(A)作為樹脂成分，於藉印刷於太陽能電池用基板上形成為遮罩之狀態下，可提高對蝕刻液之耐性。另外，藉由包含沸點為190℃以上之溶劑(B)，可抑制印刷時蝕刻遮罩用組成物(油墨)乾燥，且提高再印刷性或油墨噴出性。 The composition for an etch mask described above can be improved in resistance to an etching solution by using a novolac resin (A) excellent in acid resistance as a resin component and forming a mask on a substrate for solar cell printing. . In addition, by including the solvent (B) having a boiling point of 190 ° C or higher, drying of the composition for etching the mask (ink) during printing can be suppressed, and reprintability or ink discharge property can be improved.
且，藉由使蝕刻遮罩用組成物含界面活性劑(C)，在將該蝕刻遮罩用組成物印刷於太陽能電池用基板上時，對於所設定之印刷圖型寬度，實際上不會增大所印刷圖型之寬度，亦即，可抑制印刷時產生滲出。 Further, when the etching mask composition contains the surfactant (C), when the composition for the etching mask is printed on the solar cell substrate, the width of the printing pattern to be set is practically not Increasing the width of the printed pattern, that is, suppressing bleeding during printing.
如圖1(A)所示，於矽基板或銅、鎳、鋁等金屬基板等之太陽能電池用基板10上，使用上述蝕刻遮罩用組成物，使用網版印刷法、噴墨印刷法、輥塗佈印刷法、凸版印刷法、凹版印刷法、平版印刷法等印刷法形成遮罩圖型20。又，形成遮罩圖型20前，亦可視需要進行基板之前處理。至於前處理列舉為形成潑液性層之步驟，列舉為 例如特開2009-253145號公報所記載之步驟。接著，將遮罩圖型20加熱，烘烤遮罩圖型20。加熱條件係依據蝕刻遮罩用組成物之成分，或遮罩圖型20之膜厚等適當設定，例如在200℃歷時3分鐘。 As shown in FIG. 1(A), the composition for the etching mask is used for the solar cell substrate 10 such as a tantalum substrate or a metal substrate such as copper, nickel or aluminum, and a screen printing method or an inkjet printing method is used. A mask pattern 20 is formed by a printing method such as a roll coating printing method, a letterpress printing method, a gravure printing method, or a lithography method. Further, before the mask pattern 20 is formed, the substrate may be processed as needed. As for the pretreatment, the steps listed as forming a liquid-repellent layer are listed as For example, the procedure described in JP-A-2009-253145. Next, the mask pattern 20 is heated to bake the mask pattern 20. The heating conditions are appropriately set depending on the composition of the composition for etching the mask, or the film thickness of the mask pattern 20, for example, at 200 ° C for 3 minutes.
接著，如圖1(B)所示，使用氫氟酸與硝酸之混合酸等之蝕刻液選擇性地去除露出於遮罩圖型20之開口部之太陽能電池用基板，並蝕刻遮罩圖型20之開口部(露出部)之太陽能電池基板，而轉印遮罩圖型。 Next, as shown in FIG. 1(B), the solar cell substrate exposed to the opening of the mask pattern 20 is selectively removed using an etching solution such as a mixed acid of hydrofluoric acid and nitric acid, and the mask pattern is etched. The solar cell substrate of the opening portion (exposed portion) of 20, and the transfer mask pattern.
接著，如圖1(C)所示，經蝕刻處理後，去除遮罩圖型20。去除方法列舉為於鹼性水溶液、有機溶劑、市售之剝離液等中，在室溫浸漬5分鐘~10分鐘左右之剝離方法。鹼水溶液有氫氧化鈉水溶液、氫氧化四甲基銨(TMAH)水溶液等。有機溶劑有丙二醇單甲基醚乙酸酯(PGMEA)、二甲基亞碸(DMSO)等。至於市售之剝離液可使用有機溶劑系之HAKURI 105(東京應化工業公司製造)等。該結果，可於太陽能電池基板10上獲得對應於遮罩圖型20之凸部所轉印之圖型。又，作為形成於太陽能電池用基板上之凸部之功能列舉為電極或擴散層。 Next, as shown in FIG. 1(C), after the etching process, the mask pattern 20 is removed. The removal method is exemplified by a method of immersing in an alkaline aqueous solution, an organic solvent, a commercially available stripping solution, or the like at room temperature for about 5 minutes to 10 minutes. The aqueous alkali solution may be an aqueous solution of sodium hydroxide or an aqueous solution of tetramethylammonium hydroxide (TMAH). The organic solvent is propylene glycol monomethyl ether acetate (PGMEA), dimethyl hydrazine (DMSO) or the like. As the commercially available peeling liquid, an organic solvent-based HAKURI 105 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) or the like can be used. As a result, a pattern corresponding to the transfer of the convex portion of the mask pattern 20 can be obtained on the solar cell substrate 10. Moreover, the function as a convex part formed in the substrate for solar cells is mentioned as an electrode or a diffusion layer.
由以上步驟，可於太陽能電池用基板上形成特定圖型之凸部。上述蝕刻遮罩用組成物由於耐酸性或圖型形成精度優異，故可於太陽能電池用基板上精度良好地形成期望之圖型。又，不須經過如光微影法之複雜步驟，可藉印刷法於太陽能電池用基板上形成圖型，故使太陽能電池之製造製程簡化，且可降低太陽能電池之製造成本。 According to the above steps, the convex portion of the specific pattern can be formed on the substrate for a solar cell. Since the composition for an etching mask is excellent in acid resistance or pattern formation precision, a desired pattern can be formed accurately on a substrate for a solar cell. Moreover, the complicated steps such as the photolithography method are not required, and the pattern can be formed on the substrate for the solar cell by the printing method, so that the manufacturing process of the solar cell is simplified, and the manufacturing cost of the solar cell can be reduced.
表1中列出實施例1-4及比較例1-5之蝕刻遮罩用組成物之成分。實施例1-4及比較例1-5之蝕刻遮罩用組成物中使用之酚醛清漆樹脂(A)-1為質量平均分子量18000(m/p=60/40)之酚醛清漆樹脂。將表1所示之溶劑(B)溶解於該酚醛清漆樹脂(A)-1中，製作由實施例1-4及比較例1-5之蝕刻遮罩用組成物所成之油墨。 Table 1 lists the components of the compositions for etching masks of Examples 1-4 and Comparative Examples 1-5. The novolak resin (A)-1 used in the composition for etching masks of Examples 1-4 and Comparative Examples 1-5 was a novolak resin having a mass average molecular weight of 18,000 (m/p = 60/40). The solvent (B) shown in Table 1 was dissolved in the novolac resin (A)-1 to prepare an ink obtained from the compositions for etching masks of Examples 1-4 and Comparative Examples 1-5.
利用網版印刷將製作之各油墨印刷於矽基板上，形成500μm寬及1000μm寬之圖型。形成之圖型在200℃之加熱板上乾燥3分鐘。為確認形成之圖型之耐酸性，故浸漬於 4%氫氟酸水溶液或69%硝酸水溶液中，以光學顯微鏡觀察圖型之表面狀態。結果，針對實施例1-4，確認即使在4%氫氟酸水溶液中浸漬10分鐘，在69%硝酸水溶液中浸漬1分鐘，膜之狀態均未變化。另一方面，比較例1-5中由於因印刷擦破而難以形成正常圖型，導致無法進行耐酸性評價。 Each of the produced inks was printed on a ruthenium substrate by screen printing to form a pattern having a width of 500 μm and a width of 1000 μm. The resulting pattern was dried on a hot plate at 200 ° C for 3 minutes. In order to confirm the acid resistance of the formed pattern, it is immersed in The surface state of the pattern was observed with an optical microscope in a 4% aqueous solution of hydrofluoric acid or a 69% aqueous solution of nitric acid. As a result, with respect to Example 1-4, it was confirmed that even if immersed in a 4% hydrofluoric acid aqueous solution for 10 minutes and immersed in a 69% nitric acid aqueous solution for 1 minute, the state of the film did not change. On the other hand, in Comparative Example 1-5, it was difficult to form a normal pattern due to printing scratching, and evaluation of acid resistance could not be performed.
針對上述實施例1-4及比較例1-5之各油墨，連續進行網版印刷，並確認印刷安定性。關於印刷安定性之結果分類如下。 With respect to each of the inks of the above Examples 1-4 and Comparative Examples 1-5, screen printing was continuously performed, and printing stability was confirmed. The results regarding printing stability are classified as follows.
○：7次連續印刷時之印刷性良好(第1次至第7次之印刷圖型均無變化) ○: Good printability in 7 consecutive printings (no change in the first to seventh printing patterns)
△：7次連續印刷時之印刷性良好(印刷圖型之表面粗糙度自第1次開始緩慢增加，無印刷擦破) △: The printability was good in 7 consecutive printings (the surface roughness of the printing pattern gradually increased from the first time, and no printing was broken)
×：7次連續印刷時之印刷性不良(印刷擦破) ×: poor printability at 7 consecutive printings (printing and rubbing)
所得結果示於表1。由表1確認含沸點為190℃以上之溶劑(B)之實施例1-4之印刷性安定良好。且，確認相對於溶劑全體之溶劑(B)之含量為66.6%之比較例5之印刷安定性不良。相對於此，確認相對於溶劑全體之溶劑(B)含量為70%之實施例4之印刷安定性良好。 The results obtained are shown in Table 1. From Table 1, it was confirmed that the printing properties of Examples 1-4 containing the solvent (B) having a boiling point of 190 ° C or higher were good. Further, it was confirmed that the printing stability of Comparative Example 5 in which the content of the solvent (B) in the entire solvent was 66.6% was poor. On the other hand, it was confirmed that the printing stability of Example 4 in which the solvent (B) content of the entire solvent was 70% was good.
表2中列出實施例5-12之蝕刻遮罩用組成物之成 分。實施例5-12均含界面活性劑(C)。表3列出實施例5-12中所用之界面活性劑(C)之細節。 Table 2 lists the composition of the etching mask of Examples 5-12. Minute. Each of Examples 5-12 contained a surfactant (C). Table 3 lists the details of the surfactant (C) used in Examples 5-12.
依據「耐酸性評價」中說明之圖型形成條件，使用實施例1、5-12之各油墨，於矽基板上形成500μm寬及1000μm寬之圖型，評價印刷滲出。關於印刷滲出之評價分類如下。 According to the pattern forming conditions described in "Evaluation of Acid Resistance", the inks of Examples 1 and 5-12 were used to form patterns of 500 μm width and 1000 μm width on the ruthenium substrate, and the printing bleed was evaluated. The evaluation of printing bleed is classified as follows.
△：實際上形成之圖型之寬度A與設定之寬度B之差| A-B |為300μm以上 △: the difference between the width A of the actually formed pattern and the set width B | A-B | is 300 μm or more
○：實際上形成之圖型之寬度A與設定之寬度B之差| A-B |為60μm以上300μm以下 ○: the difference between the width A of the pattern actually formed and the width B of the setting | A-B | is 60 μm or more and 300 μm or less
◎：實際上形成之圖型之寬度A與設定之寬度B之差| A-B |未達60μm ◎: the difference between the width A of the actually formed pattern and the set width B | A-B | less than 60 μm
所得結果示於表4。由表4所示之印刷滲出之評價結果，確認實施例1、實施例5-12之任一種油墨均具有抑制印刷滲出之效果。尤其，使用BYK-SILCLEAN3720(聚醚改質之含羥基之聚二甲基矽氧烷)或氟系之APX-4082B作為界面活性劑(C)之實施例9-12(界面活性劑(C)之含量：0.1、0.01、0.001質量%)確認顯著抑制了印刷滲出。 The results obtained are shown in Table 4. From the evaluation results of the printing bleed shown in Table 4, it was confirmed that any of the inks of Example 1 and Examples 5 to 12 had an effect of suppressing printing bleeding. In particular, Example 9-12 (surfactant (C)) using BYK-SILCLEAN 3720 (polyether-modified hydroxyl-containing polydimethyloxane) or fluorine-based APX-4082B as surfactant (C) Content: 0.1, 0.01, 0.001% by mass) It was confirmed that printing bleeding was remarkably suppressed.
表5列出實施例13-15、比較例6之蝕刻遮罩用組成物之成分。各例均含界面活性劑(C)。表5中，(A)-2為質量平均分子量2150、(m/p=60/40)之酚醛清漆樹脂，KF-353為信越化學工業(股)公司製造、矽系，主成分：聚醚改質之甲基聚矽氧烷，不揮發分100wt%之界面活性劑。 Table 5 lists the components of the compositions for etching masks of Examples 13-15 and Comparative Example 6. Each case contained a surfactant (C). In Table 5, (A)-2 is a novolak resin having a mass average molecular weight of 2,150 and (m/p=60/40), and KF-353 is a product manufactured by Shin-Etsu Chemical Co., Ltd., a main component: polyether. The modified methyl polyoxyalkylene has a non-volatile content of 100% by weight of a surfactant.
以噴墨印刷機(製品名「MID-500C」，武藏工程股份有限公司製造)，以下述條件將各例之蝕刻遮罩用組成物噴出於經前處理之具有寬度4μm高度4μm之紋路表面之基板上，且在200℃烘烤處理3分鐘。分別觀測進行3次或5次重複塗佈時之圖型與膜厚。均可形成約30μm之線圖型，可確認印刷性良好。 Each of the etch mask compositions of the respective examples was sprayed by a preliminarily processed textured surface having a width of 4 μm and a height of 4 μm by an ink jet printer (product name "MID-500C", manufactured by Musashi Engineering Co., Ltd.) under the following conditions. On the substrate, and baked at 200 ° C for 3 minutes. The pattern and film thickness at the time of repeated application of 3 or 5 times were observed. A line pattern of about 30 μm can be formed, and it is confirmed that the printability is good.
印刷頻度(頻率)：3000Hz Printing frequency (frequency): 3000Hz
印刷台之溫度：80℃ Printing table temperature: 80 ° C
印刷設計：1像素×1線 Printing design: 1 pixel × 1 line
印刷頭：KM512M(14pl) Print head: KM512M (14pl)
針對所製作之上述圖型，浸漬於4%氫氟酸水溶液或69%硝酸水溶液中，以光學顯微鏡觀察圖型之表面狀態。其結果，可確認所有膜狀態均未變化。 The above-mentioned pattern produced was immersed in a 4% hydrofluoric acid aqueous solution or a 69% nitric acid aqueous solution, and the surface state of the pattern was observed with an optical microscope. As a result, it was confirmed that all the film states did not change.
以噴墨印刷機(製品名「MID-500C」，武藏工程股份有限公司製造)，以下述條件將各例之蝕刻遮罩用組成物噴出於經前處理之具有寬度4μm高度4μm之紋路表面之基板上，在200℃烘烤處理3分鐘。進行初次噴出後， 間隔1分鐘、5分鐘後再度進行噴出，以下述基準進行評價。所得結果示於表6。 Each of the etch mask compositions of the respective examples was sprayed by a preliminarily processed textured surface having a width of 4 μm and a height of 4 μm by an ink jet printer (product name "MID-500C", manufactured by Musashi Engineering Co., Ltd.) under the following conditions. On the substrate, it was baked at 200 ° C for 3 minutes. After the initial squirt, The ejection was again performed after 1 minute and 5 minutes, and the evaluation was performed based on the following criteria. The results obtained are shown in Table 6.
○：獲得如印刷設計之圖型之情況 ○: Obtaining a pattern like a print design
×：無法獲得如印刷設計之圖型之情況 ×: Unable to obtain the pattern of the print design
印刷頻度(頻率)：4255Hz Printing frequency (frequency): 4255Hz
印刷台之溫度：80℃ Printing table temperature: 80 ° C
印刷設計：1像素×512線 Printing design: 1 pixel × 512 lines
印刷頭：KM512M(14pl) Print head: KM512M (14pl)
由以上之結果，可確認本發明之實施例13-15之蝕刻遮罩用組成物，除耐酸性以外，以噴墨進行之印刷性亦良好。又，實施例14儘管固體成分濃度低於比較例6，但亦形成同等以上厚度之印刷膜。 From the above results, it was confirmed that the composition for an etching mask of Example 13-15 of the present invention was excellent in printability by inkjet in addition to acid resistance. Further, in Example 14, although the solid content concentration was lower than that of Comparative Example 6, a printing film having a thickness equal to or greater than that of the above was formed.
10‧‧‧太陽能電池用基板 10‧‧‧Solid cell substrate
20‧‧‧遮罩圖型 20‧‧‧ mask pattern
圖1(A)至圖1(C)為顯示對基板之圖型形成步驟 之概略剖面圖。 1(A) to 1(C) are diagrams showing a pattern forming step of a substrate A schematic cross-sectional view.
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