TW202129078A - 蝕刻液組成物及蝕刻方法 - Google Patents
蝕刻液組成物及蝕刻方法 Download PDFInfo
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- TW202129078A TW202129078A TW109143359A TW109143359A TW202129078A TW 202129078 A TW202129078 A TW 202129078A TW 109143359 A TW109143359 A TW 109143359A TW 109143359 A TW109143359 A TW 109143359A TW 202129078 A TW202129078 A TW 202129078A
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- Prior art keywords
- etching
- acid
- silver
- etching solution
- solution composition
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- ZRVXFJFFJZFRLQ-UHFFFAOYSA-M tetramethylazanium;iodate Chemical compound [O-]I(=O)=O.C[N+](C)(C)C ZRVXFJFFJZFRLQ-UHFFFAOYSA-M 0.000 description 1
- ZCWKIFAQRXNZCH-UHFFFAOYSA-M tetramethylazanium;perchlorate Chemical compound C[N+](C)(C)C.[O-]Cl(=O)(=O)=O ZCWKIFAQRXNZCH-UHFFFAOYSA-M 0.000 description 1
- HLQAWDQQEJSALG-UHFFFAOYSA-M tetramethylazanium;periodate Chemical compound C[N+](C)(C)C.[O-]I(=O)(=O)=O HLQAWDQQEJSALG-UHFFFAOYSA-M 0.000 description 1
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/30—Acidic compositions for etching other metallic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Computer Hardware Design (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
Abstract
本發明所提供的蝕刻液組成物，係可一邊抑制側蝕刻與殘渣的發生，一邊對含銀層施行蝕刻。屬於對含銀層施行蝕刻所使用的蝕刻液組成物。其含有：(A)成分：氧化劑0.1~20質量%、(B)成分：(i)二羧酸之銨鹽、及(ii)上述二羧酸與胺化合物或銨化合物的組合中之至少任一成分0.5~40質量%、以及水；且，上述二羧酸係草酸、或無取代或者被羥基取代之具碳數2以下之烯烴鏈的有機酸。
Description
本發明係關於對含銀層施行蝕刻所使用的蝕刻液組成物、及使用其之蝕刻方法。
表面已形成電路的印刷佈線板或薄膜，被廣泛使用於安裝電子零件或半導體元件等。近年針對此種印刷佈線板等所使用的佈線，使用導電性或熱傳導性等性質優異之銀或銀合金(以下統稱為「銀材料」)的機會正增加中。
製造印刷佈線板的方法大多採取利用濕式蝕刻形成銀材料佈線的方法。關於此種濕式蝕刻所使用的蝕刻液組成物，截至目前已有多數報告。例如專利文獻1提案有：經調配磷酸、硝酸、醋酸、及水的蝕刻液組成物。又，專利文獻2提案有：含有以硫酸鐵(III)為有效成分之酸性水溶液所構成的蝕刻液。又，專利文獻3提案有：含有硝酸、硫酸、氯化氫、及水的蝕刻液組成物。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本專利特開2004-176115號公報
[專利文獻2]日本專利特開平10-060671號公報
[專利文獻3]日本專利特開2017-171992號公報
(發明所欲解決之問題)
然而，佈線圖案微細化演進的結果，若使用習知蝕刻液組成物對銀材料施行蝕刻，會有側蝕刻量增加的傾向，由銀材料所形成的佈線部分會有容易發生斷線的情況。
再者，針對佈線部分以外的區域，期望利用蝕刻除去銀材料。但是，若使用習知蝕刻液組成物對已微細化佈線圖案施行蝕刻，則容易發生銀材料的殘渣。所以，會有因生成的銀材料殘渣導致電路佈線容易發生短路等不良情況產生。側蝕刻量的增加或殘渣的發生會大幅損及電路佈線的電氣連接可靠性。
緣是，本發明係有鑑於習知技術的問題而完成，其課題在於提供：可一邊抑制側蝕刻與殘渣的發生，一邊對含銀層施行蝕刻的蝕刻液組成物。又，本發明的課題在於提供：使用該蝕刻液組成物，可一邊抑制側蝕刻與殘渣的發生，一邊對含銀層施行蝕刻的蝕刻方法。
(解決問題之技術手段)
本發明者等為解決上述課題經深入鑽研，結果發現依特定濃度含有特定成分的蝕刻液組成物可解決上述課題，遂完成本發明。
即，根據本發明所提供的蝕刻液組成物，係對含銀層施行蝕刻所使用的蝕刻液組成物，其含有：(A)成分：氧化劑0.1~20質量%、(B)成分：(i)二羧酸之銨鹽、及(ii)上述二羧酸與胺化合物或銨化合物的組合中之至少任一成分0.5~40質量%、以及水；且，上述二羧酸係草酸、或無取代或者被羥基取代之具碳數2以下之烯烴鏈的有機酸。
本發明中，上述氧化劑較佳係過氧化氫。
本發明中，二羧酸較佳係琥珀酸。
本發明中，(B)成分較佳係琥珀酸銨。
本發明的蝕刻液組成物係適用為對含有銀或銀合金的含銀層施行蝕刻的組成物。
再者，根據本發明所提供的蝕刻方法，係包括有：使用上述蝕刻液組成物對含銀層施行蝕刻的步驟。
(對照先前技術之功效)
根據本發明可提供：能一邊抑制側蝕刻與殘渣的發生，一邊對含銀層施行蝕刻的蝕刻液組成物。又，根據本發明可提供：使用該蝕刻液組成物，一邊抑制側蝕刻與殘渣的發生，一邊對含銀層施行蝕刻的蝕刻方法。
以下，針對本發明實施形態進行具體說明。本說明書中的所謂「蝕刻」係指利用化學藥物等之腐蝕作用施行塑形或表面加工的技法。具體而言，可舉例如：將所使用素材表面的必要部分利用蝕刻光阻劑被覆，且使用蝕刻液組成物將不需要部分施行溶解/侵蝕而加工為所需形狀的手法。
本說明書中的「含銀層」係只要含有銀的層便可。銀係除了例如：天然銀(銀單體)、氧化銀等、銀奈米粒子、銀奈米板、及銀奈米線等銀成分之外；亦可為以銀為主體且含有微量其他金屬(例如：鋁、矽、鈦、鉻、銅、鋅、鍺、銦、錫、鈀、白金、金、及釹等)的銀合金。
「含銀層」的形狀並無特別的限定，可為例如：金屬膜、金屬板、金屬箔、金屬粒子、以及含有樹脂與金屬的複合物。本說明書中的「金屬」係指含有上述銀的金屬。「含銀層」較佳係上述銀含有1質量%以上、更佳係含有5質量%以上。
本發明一實施形態的蝕刻液組成物係對含銀層施行蝕刻所使用的組成物(蝕刻液)，且係含有以下(A)成分、(B)成分、及水的水溶液：
(A)成分：氧化劑
(B)成分：(i)二羧酸之銨鹽、及(ii)上述二羧酸與胺化合物或銨化合物的組合中之至少任一成分
(A)成分係氧化劑。氧化劑係可舉例如：正甲基
啉氧化物、過氧化苯甲醯、過氧化四丁銨單硫酸、臭氧、三氯化鐵、過錳酸過氧硼酸、過氯酸、過氧硫酸、過氧二硫酸銨(ammonium peroxydisulfate)、過醋酸、過氧化氫脲(hydrogen peroxide urea)、硝酸、亞氯酸銨、氯酸銨、碘酸銨、過硼酸銨、過氯酸銨、過碘酸銨、過硫酸銨、亞氯酸四甲銨、氯酸四甲銨、碘酸四甲銨、過硼酸四甲銨、過氯酸四甲銨、過碘酸四甲銨、過硫酸四甲銨、及過氧化氫等。該等氧化劑係可單獨使用1種或組合使用2種以上。從獲得更顯著效果的觀點，氧化劑較佳係過氧化氫。
蝕刻液組成物中的(A)成分濃度係0.1~20質量%、較佳係0.5~10質量%、更佳係0.5~5質量%。若(A)成分濃度未滿0.1質量%，則蝕刻速度明顯降低，導致生產性降低，且容易發生殘渣。另一方面，若(A)成分濃度超過20質量%，則蝕刻速度較難控制。
(B)成分係(i)二羧酸之銨鹽、及(ii)上述二羧酸與胺化合物或銨化合物的組合中之至少任一成分。
而，構成該(B)成分的二羧酸係草酸、或無取代或者被羥基取代之具碳數2以下之烯烴鏈的有機酸。無取代或者被羥基取代之具碳數2以下之烯烴鏈的有機酸係可舉例如：酒石酸、丙二酸、及琥珀酸等。該等有機酸係可單獨使用1種或組合使用2種以上。從獲得更顯著效果的觀點，二羧酸較佳係琥珀酸。
再者，(B)成分較佳係二羧酸的銨鹽。二羧酸的銨鹽係可舉例如：草酸銨、琥珀酸銨、及酒石酸銨等。該等二羧酸的銨鹽係可單獨使用1種或組合使用2種以上。尤其從獲得更顯著效果的觀點，(B)成分較佳係琥珀酸銨。
胺化合物係可舉例如：伸乙二胺、二伸乙三胺、三伸乙四胺、四伸乙五胺、五伸乙六胺、六伸乙七胺、七伸乙八胺、八伸乙九胺、九伸乙十胺、伸丁二胺、五亞甲二胺、六亞甲二胺、七亞甲二胺、四甲基伸乙二胺、五甲基二伸乙三胺、四甲基三伸乙四胺、五甲基三伸乙四胺、及六甲基三伸乙四胺等鏈狀胺；環丙胺、環丁胺、環戊胺、環己胺、環庚胺、環辛胺、環壬胺、環癸胺、環十一胺、及環十二胺之脂環式胺；苯胺、2-甲基苯胺、3-甲基苯胺、2,3-二甲基苯胺、4-甲基苯胺、5-甲基苯胺、2-乙基苯胺、3-乙基苯胺、4-乙基苯胺、5-乙基苯胺、2,4-二甲基苯胺、2,5-二甲基苯胺、2-丙基苯胺、及2-丁基苯胺等芳香族胺等。該等胺化合物係可單獨使用1種或組合使用2種以上。
銨化合物係可舉例如：氨、碳酸氫銨、碳酸銨、氫氧化四甲銨、及氫氧化四乙銨等。該等銨化合物係可單獨使用1種或組合使用2種以上。
蝕刻液組成物中的(B)成分濃度係0.5~40質量%、較佳係1~30質量%、更佳係2~10質量%。若(B)成分濃度未滿0.5質量%，則較難抑制側蝕刻與殘渣的發生。另一方面，若(B)成分濃度超過40質量%，會有(B)成分不易溶解的情況。
本實施形態的蝕刻液組成物係含有水。即，本實施形態的蝕刻液組成物係(A)成分與(B)成分溶解於水中而成的水溶液。蝕刻液組成物在25℃下的pH較佳係5.5~10。若蝕刻液的pH在上述數值範圍外，則含銀層的蝕刻控制略為困難。另外，從提升所形成佈線直線性的觀點，蝕刻液在25℃下的pH更佳係pH6~9。
本實施形態的蝕刻液組成物中，在不致損及本發明效果之範圍內，視需要可含有周知的添加劑。可含有的添加劑係可舉例如：還原劑、界面活性劑、安定化劑、可溶化劑、消泡劑、比重調節劑、黏度調節劑、潤濕性改善劑、聚烷二醇、有機酸、胺基酸類、唑類、嘧啶類、硫脲類、胺類、烷基吡咯啶酮類、有機螯合劑、聚丙烯醯胺類、過硫酸鹽、及pH調節劑等。蝕刻液組成物中的添加劑濃度，若以蝕刻液組成物全體為基準，較佳係0.001~50質量%。
當蝕刻液組成物的蝕刻速度較快時，最好添加還原劑。還原劑係可舉例如：能溶解於蝕刻液組成物中的金屬粉、亞硝酸鈉、及次亞磷酸鈉等。
界面活性劑係可舉例如：氟烷基甜菜
、及氟烷基聚氧乙烯醚等氟系兩性界面活性劑；非離子系界面活性劑等。
安定化劑係可舉例如：2-胺基-2-甲基-1-丙醇、1-胺基-2-丙醇、2-胺基乙醇、及氫氧化四甲銨等胺化合物；1,2,4-1H-三唑、1H-苯并三唑、5-甲基-1H-苯并三唑、3-胺基-1H-1,2,4-三唑、1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、及5-胺基-1H-四唑等唑類；苯基脲、烯丙基脲、1,3-二甲脲、及硫脲等脲類；酚磺酸、苯磺酸、及甲酚磺酸等芳香族磺酸類；甲磺酸、及乙磺酸等烷烴磺酸類；苯基乙二醇、1-丙醇、2-丙醇、及2-丁氧基乙醇等醇類等。
可溶化劑較佳係可與水混合，且能促進蝕刻殘留物除去的成分。可溶化劑係可舉例如：環丁碸、N-甲基吡咯啶酮、及二甲亞碸等。
消泡劑係可舉例如：矽消泡劑、長鏈醇消泡劑、脂肪酸酯消泡劑、金屬皂消泡劑、及環氧乙烷-環氧丙烷共聚合體等。
比重調節劑係可使用使比重調整用的物質溶解於溶媒中的溶液、或稀釋水。比重調整用的物質係只要該溶液不會使含銀層腐蝕或剝離便可使用。比重調整用的物質係可舉例如：純水、離子交換水、自來水、蔗糖等醣類、食用鹽、及脲等。
黏度調節劑較佳係使用與蝕刻液組成物具相溶性者。黏度調節劑係可舉例如：山梨糖醇、低分子量聚乙烯吡咯啶酮、聚乙烯醇、羥乙基纖維素、羥丙基纖維素之水溶液、羥丙基纖維素之溶膠、及稀釋水等。
潤濕性改善劑係在可輕易排除含銀層的狹溝等之中所存在空氣，且能獲得脫脂效果等之目的下，添加於蝕刻液組成物中。
聚烷二醇係可舉例如：聚乙二醇；聚乙二醇二甲醚；在乙二醇、丙二醇、1,3-丁醇、1,4-丁醇等二醇中，嵌段或無規加成環氧乙烷、環氧丙烷的聚烷二醇等。
有機酸係可舉例如：蟻酸、醋酸、丙酸、丁酸、吉草酸、己酸、丙烯酸、巴豆酸、異巴豆酸、草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、甘醇酸、乳酸、磺胺酸、菸鹼酸、抗壞血酸、羥基三甲基乙酸、4-戊酮酸、及β-氯丙酸等。
胺基酸類係可舉例如：甘胺酸、丙胺酸、纈胺酸、白胺酸、絲胺酸、苯基丙胺酸、色胺酸、麩胺酸、天冬胺酸、離胺酸、及精胺酸、組胺酸等胺基酸；該等胺基酸的鹼金屬鹽及銨鹽等。
唑類係可舉例如：咪唑、2-甲基咪唑、2-十一基-4-甲基咪唑、2-苯基咪唑、及2-甲基苯并咪唑等烷基咪唑類；苯并咪唑、2-甲基苯并咪唑、2-十一基苯并咪唑、2-苯基苯并咪唑、及2-巰基苯并咪唑等苯并咪唑類；1,2,3-三唑、1,2,4-三唑、5-苯基-1,2,4-三唑、5-胺基-1,2,4-三唑、1,2,3-苯并三唑、1-胺基苯并三唑、4-胺基苯并三唑、1-雙胺基甲基苯并三唑、1-甲基-苯并三唑、甲苯三唑、1-羥基苯并三唑、5-甲基-1H-苯并三唑、及5-氯苯并三唑等三唑類；1H-四唑、5-胺基-1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-巰基-1H-四唑、1-苯基-5-巰基-1H-四唑、1-環己基-5-巰基-1H-四唑、及5,5'-雙-1H-四唑等四唑類；苯并噻唑、2-巰基苯并噻唑、2-苯基噻唑、2-胺基苯并噻唑、2-胺基-6-硝基苯并噻唑、2-胺基-6-甲氧基苯并噻唑、及2-胺基-6-氯苯并噻唑等噻唑類等。
嘧啶類係可舉例如：二胺基嘧啶、三胺基嘧啶、四胺基嘧啶、及巰基嘧啶等。
硫脲類係可舉例如：硫脲、乙烯硫脲、硫二乙二醇、及硫醇等。
胺類係可舉例如：二戊胺、二丁胺、三乙胺、三戊胺、單乙醇胺、二乙醇胺、三乙醇胺、單異丙醇胺、二異丙醇胺、三異丙醇胺、乙醇異丙醇胺、二乙醇異丙醇胺、乙醇二異丙醇胺、聚烯丙胺、聚乙烯吡啶、及該等的鹽酸鹽等。
烷基吡咯啶酮類係可舉例如：N-甲基-2-吡咯啶酮、N-乙基-2-吡咯啶酮、N-丙基-2-吡咯啶酮、N-丁基-2-吡咯啶酮、N-戊基-2-吡咯啶酮、N-己基-2-吡咯啶酮、N-庚基-2-吡咯啶酮、及N-辛基-2-吡咯啶酮等。
有機螯合劑係可舉例如：伸乙二胺四醋酸、二伸乙三胺五醋酸、三伸乙四胺六醋酸、四伸乙五胺七醋酸、五伸乙六胺八醋酸、氮基三醋酸、及該等的鹼金屬(較佳係鈉)鹽等胺基羧酸系螯合劑；羥基亞乙基二膦酸、氮基三亞甲基膦酸、膦醯基丁烷三羧酸、及該等的鹼金屬(較佳係鈉)鹽等膦酸系螯合劑；草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、順丁烯二酸、反丁烯二酸、蘋果酸、酒石酸、檸檬酸、該等的酐、及該等的鹼金屬(較佳係鈉)鹽等二元以上的羧酸化合物；或二元以上的羧酸化合物脫水而成的單酐或二酐等。蝕刻液組成物中的有機螯合劑濃度可以係例如0.01~40質量%。
聚丙烯醯胺類係可舉例如：聚丙烯醯胺、及第三丁基丙烯醯胺磺酸等。
過硫酸鹽係可舉例如：過硫酸銨、過硫酸鈉、及過硫酸鉀等。
pH調節劑係含有鹼或酸的成分。鹼係可舉例如：胺、二乙二醇胺、三乙醇胺、氫氧化四丁鏻、一級胺化合物、二級胺化合物、及三級胺化合物等。酸係可舉例如：硫酸、硝酸、磷酸、氫氟酸、及氫溴酸等無機酸；羧酸、胺基酸、羥基羧酸、及聚羧酸等有機酸等。
本實施形態之蝕刻液組成物的具體用途係可舉例如：含銀層用的去除劑、表面平滑化劑、表面粗化劑、圖案形成用藥劑、基體上微量附著的銀成分洗淨液等。
其次，針對本發明一實施形態的蝕刻方法進行說明。本實施形態的蝕刻方法係包括有：使用前述蝕刻液組成物對含銀層施行蝕刻的步驟。更具體而言，首先，準備已在基板上的既定區域形成含銀層(例如金屬膜等)的材料，使用蝕刻光阻劑將含銀層的必要部分施行遮罩而形成遮罩區域。其次，將遮罩區域以外之區域(非遮罩區域)的含銀層，利用前述蝕刻液組成物施行蝕刻而除去。對非遮罩區域之含銀層的蝕刻方法並無特別的限定，可使用一般的蝕刻方法。例如：利用浸漬式、噴霧式、旋轉式等施行的蝕刻方法。又，對非遮罩區域之含銀層施行蝕刻的條件無特別的限定，可採用例如：批次式、流動式、利用蝕刻劑之氧化還原電位、比重、酸濃度進行自動控制式等周知一般的各種方式。
當利用浸漬式蝕刻方法對基板上已形成含銀層的材料施行蝕刻時，藉由將該材料在適當蝕刻條件下浸漬於蝕刻液組成物中之後再拉起，便可對基板上的含銀層施行蝕刻。
浸漬式蝕刻方法的蝕刻條件係只要配合被蝕刻材料的含銀層之形狀或膜厚等再行任意設定便可。施行一般的蝕刻時，蝕刻溫度較佳係10~40℃、更佳係20~40℃。蝕刻液組成物的溫度會因反應熱而上升。所以，視需要，最好將蝕刻液組成物的溫度利用公知手段進行溫度控制維持於上述範圍內。又，蝕刻時間係只要設定為能完成蝕刻的充分時間便可，並無特別的限定。例如，若含銀層的膜厚係1nm~1μm程度，則只要依上述溫度範圍進行10秒~1小時程度的蝕刻便可。
當利用噴霧式蝕刻方法對基板上已形成含銀層的材料施行蝕刻時，藉由將蝕刻液組成物依適當條件朝材料施行噴霧，便可對基板上的含銀層施行蝕刻。
噴霧式蝕刻方法時的蝕刻條件係只要配合含銀層的形狀或膜厚等再行任意設定便可。例如，施行一般的蝕刻時，將蝕刻液組成物施行噴霧時的噴霧壓係可從0.01~1.0MPa之範圍中選擇，較佳係0.02~0.1MPa之範圍、更佳係0.03~0.08MPa之範圍。若將噴霧壓設為0.03~0.08MPa之範圍，可使佈線部分的含銀層之上部寬度與下部寬度的差非常小，故特佳。蝕刻溫度較佳係10~50℃之範圍、更佳係20~50℃之範圍。蝕刻液組成物的溫度會因反應熱而上升。所以，視需要，最好將蝕刻液組成物的溫度利用公知手段進行溫度控制維持於上述範圍內。又，蝕刻時間係只要設定為能完成蝕刻的充分時間便可，並無特別的限定。例如，若膜厚為1nm~1μm程度，則只要依上述溫度範圍施行10秒~1小時程度的蝕刻便可。
本實施形態的蝕刻方法，為使因重複施行蝕刻所導致的蝕刻液組成物劣化能復原，最好更進一步包括有對蝕刻液組成物添加補充液的步驟。特別係自動控制式蝕刻的情況，若在蝕刻裝置中預先設定補充液，便可對蝕刻液組成物適當添加補充液。補充液係可使用例如含有前述(A)成分或(B)成分的水溶液。各成分的濃度係只要設為蝕刻液組成物中各成分濃度的3~20倍程度便可。在該補充液中，視需要可在蝕刻液組成物中添加必需或任意使用的前述各成分。
根據使用上述蝕刻液組成物的本發明一實施形態之蝕刻方法，便可抑制側蝕刻而形成精密的電路佈線。所以，本發明一實施形態的蝕刻液組成物係除適用於觸控感測器用電極形成等印刷佈線基板之外，亦可適用於要求細節距的封裝用基板、COF、TAB用途的移除法及半加成法的電路形成。
[實施例]
以下，使用實施例與比較例，針對本發明進行更詳細說明。然而，本發明並不因以下實施例等而受任何限制。
＜蝕刻液組成物之調製＞
(實施組成物1~9、比較組成物1~5)
將各成分依表1所示配方進行混合，而調製得蝕刻液組成物(實施組成物1~9及比較組成物1~5)。表1中的「pH值」係剛製造後的蝕刻液組成物在25℃下的pH值。又，表1中括號內的數值係以蝕刻液組成物全體為基準的各成分含有量(質量%)。
| [表1] | |||||
| (A)成分 | (B)成分 | 水 | 其他成分 | pH值 | |
| 實施組成物1 | A-1(0.175) | B-1(5) | 水(94.825) | － | 6.4 |
| 實施組成物2 | A-1(0.35) | B-1(2) | 水(97.15) | C-1(0.50) | 6.4 |
| 實施組成物3 | A-1(3.5) | B-1(30) | 水(66) | C-1(0.50) | 6.6 |
| 實施組成物4 | A-1(0.35) | B-1(5) | 水(93.65) | － | 9 |
| B-3(1) | |||||
| 實施組成物5 | A-1(0.35) | B-2(4.5) | 水(93.645) | C-1(0.2) | 6.1 |
| B-4(1.305) | |||||
| 實施組成物6 | A-1(0.35) | B-2(4) | 水(90.45) | C-1(0.2) | 6.3 |
| B-5(5) | |||||
| 實施組成物7 | A-1(0.35) | B-6(5) | 水(94.15) | C-1(0.5) | 6.3 |
| 實施組成物8 | A-1(0.35) | B-7(5) | 水(94.15) | C-1(0.5) | 6.4 |
| 實施組成物9 | A-1(0.70) | B-1(5) | 水(93.30) | C-1(0.5) | 5.7 |
| B-2(0.5) | |||||
| 比較組成物1 | A-1(0.35) | B-2(5) | 水(94.65) | － | 2.2 |
| 比較組成物2 | A-1(0.35) | b-1(5) | 水(94.65) | － | 5 |
| 比較組成物3 | A-1(0.35) | b-2(6) | 水(93.45) | C-1(0.2) | 7 |
| 比較組成物4 | A-1(0.35) | b-3(6) | 水(93.45) | C-1(0.2) | 6.8 |
| 比較組成物5 | A-1(0.35) | b-4(6) | 水(93.45) | C-1(0.2) | 7.2 |
＜蝕刻方法＞
(實施例1~9、比較例1~5)
準備將厚100nm之由銀-鈀-銅合金(製品名「APC」、Furuya 金屬公司製)所構成層(含銀層)積層於玻璃基板上的基體。在該基體的含銀層上，使用負型乾膜形成寬60μm、開口部60μm的光阻圖案後，裁切為50mm×50mm之大小而獲得測試片。對所獲得測試片分別使用所調製的蝕刻液組成物，依35℃、噴霧壓0.05MPa、及既定蝕刻處理時間(表2)的條件，利用噴霧法施行蝕刻，而形成評價用圖案。另外，關於比較例1與比較例2，即使施行180秒以上的蝕刻處理，仍無法形成目標形狀的圖案。
＜評價＞
(1)S.E.寬
使用雷射顯微鏡，測量蝕刻處理前光阻圖案的間隙寬(μm)、以及經蝕刻處理後剝離光阻圖案所觀察到的佈線間之間隙寬(μm)。然後，由下式(1)計算出S.E.寬(μm)。結果示於表2。
S.E.寬(μm)=(A-B)/2 ・・・(1)
A：光阻圖案之間隙寬(μm)
B：佈線間之間隙寬(μm)
(2)殘渣
經蝕刻處理後剝離光阻圖案，使用場發射型掃描電子顯微鏡(FE-SEM)，確認佈線部分的含銀層表面有無殘渣。無法確認到殘渣的情況評價為「無」，可確認到殘渣的情況評價為「有」。結果示於表2。
| [表2] | ||||
| 蝕刻液組成物 | 蝕刻處理時間[秒] | S.E.寬 [μm] | 殘渣 | |
| 實施例1 | 實施組成物1 | 90 | 0.1 | 無 |
| 實施例2 | 實施組成物2 | 50 | 0.3 | 無 |
| 實施例3 | 實施組成物3 | 35 | 0.2 | 無 |
| 實施例4 | 實施組成物4 | 40 | 0.3 | 無 |
| 實施例5 | 實施組成物5 | 105 | 0.3 | 無 |
| 實施例6 | 實施組成物6 | 90 | 0.1 | 無 |
| 實施例7 | 實施組成物7 | 35 | 0.4 | 無 |
| 實施例8 | 實施組成物8 | 45 | 0.3 | 無 |
| 實施例9 | 實施組成物9 | 120 | 0.2 | 無 |
| 比較例1 | 比較組成物1 | 180＜ | － | － |
| 比較例2 | 比較組成物2 | 180＜ | － | － |
| 比較例3 | 比較組成物3 | 40 | 0.9 | 有 |
| 比較例4 | 比較組成物4 | 90 | 1.2 | 有 |
| 比較例5 | 比較組成物5 | 45 | 1.3 | 有 |
由表2所示結果得知，若使用含有以醋酸銨、己二酸銨、或檸檬酸三銨為(B)成分的蝕刻液組成物施行蝕刻，則側蝕刻量會增加，且在含銀層表面會發生殘渣(比較例3~5)。又，得知雖含有以琥珀酸或琥珀酸鈉為(B)成分，但未與胺化合物或銨化合物組合的情況，或非為銨鹽的情況，幾乎無法蝕刻(比較例1及2)。相對於此，得知使用實施組成物1~9的蝕刻液組成物進行蝕刻時，可抑制側蝕刻量，且不會發生殘渣，可形成良好的電路佈線(實施例1~9)。
Claims (6)
- 一種蝕刻液組成物，係對含銀層施行蝕刻所使用的蝕刻液組成物，其含有： (A)成分：氧化劑0.1~20質量%； (B)成分：(i)二羧酸之銨鹽、及(ii)上述二羧酸與胺化合物或銨化合物的組合中之至少任一成分0.5~40質量%；以及 水；且， 上述二羧酸係草酸、或無取代或者被羥基取代之具碳數2以下之烯烴鏈的有機酸。
- 如請求項1之蝕刻液組成物，其中，上述氧化劑係過氧化氫。
- 如請求項1或2之蝕刻液組成物，其中，上述二羧酸係琥珀酸。
- 如請求項1或2之蝕刻液組成物，其中，上述(B)成分係琥珀酸銨。
- 如請求項1或2之蝕刻液組成物，其中，上述含銀層係含有銀或銀合金。
- 一種蝕刻方法，係包括有：使用請求項1至5中任一項之蝕刻液組成物對含銀層施行蝕刻的步驟。
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