TWI779028B - 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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- TWI779028B TWI779028B TW107114896A TW107114896A TWI779028B TW I779028 B TWI779028 B TW I779028B TW 107114896 A TW107114896 A TW 107114896A TW 107114896 A TW107114896 A TW 107114896A TW I779028 B TWI779028 B TW I779028B
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- etching solution
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- 238000005530 etching Methods 0.000 title claims abstract description 123
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims description 30
- 239000007788 liquid Substances 0.000 title description 13
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- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 239000010949 copper Substances 0.000 claims abstract description 48
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- -1 iron (III) ions Chemical class 0.000 claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
- 239000002184 metal Substances 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
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- 229920002401 polyacrylamide Chemical class 0.000 description 3
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 1
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- 239000003607 modifier Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 150000003573 thiols Chemical class 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
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- 239000010937 tungsten Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
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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
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Abstract
本發明所提供的蝕刻液組成物，係即使統括對含有銅系層、與含鎳及鉻中至少其中一者之金屬系層的積層體施行蝕刻的情況，仍可形成窄化幅度少、直線性佳、且抑制較大缺損發生的細線。
本發明的蝕刻液組成物，係用於對含有從銅、鎳及鉻所構成群組中選擇至少1種金屬之層施行蝕刻者。該蝕刻液組成物係含有：(A)鐵(III)離子0.1~10質量%；(B)氯化物離子0.1~10質量%；(C)甲酸離子0.01~5質量%；(D)從下述一般式(1)所示化合物與碳原子數1~4之直鏈或分支狀醇所構成群組中選擇至少1種化合物0.01~10質量%；(E)從下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、及由二元以上羧酸化合物施行脫水的單酐與二酐所構成群組中選擇至少1種化合物0.01~10質量%；以及水。
Description
本發明係關於蝕刻液組成物、及使用其之蝕刻方法。更詳言之，係關於用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層施行蝕刻的蝕刻液組成物，及使用其之蝕刻方法。
用於對含有銅、鎳、及鉻中至少任一者之層施行蝕刻的濕式蝕刻相關技術，已知有各種技術。
例如專利文獻1所提案的蝕刻液組成物，係用於統括對由氧化銦系被膜與金屬系被膜所構成積層膜施行蝕刻，含有：鐵(III)離子成分、氯化氫成分、及特定化合物成分的水溶液。專利文獻1揭示有：當利用該蝕刻液組成物，對含有氧化銦錫(ITO)膜與銅(Cu)膜的積層膜施行統括蝕刻時，在ITO膜與Cu膜間不致發生較大梯度，且窄化幅度少，能獲得直線性佳的細線。
專利文獻2所揭示的蝕刻液，係能提升與樹脂等被黏材間之密接性的不銹鋼用蝕刻液，含有：酸、鐵(III)離子、鹵化物離子、兩性界面活性劑、及特定金屬離子。
再者，專利文獻3所揭示的蝕刻液，係恆範鋼合金用蝕刻液，含有：氯化銅(II)或三氯化鐵、鹽酸、聚乙二醇衍生物、以及蠟或防銹油等親油性碳氫化合物類。
再者，專利文獻4所揭示的蝕刻劑，係含鉻基材用蝕刻劑組成物，含有鐵氰化鉀(potassium ferricyanide)與螯合劑。
[專利文獻1]國際公開第2013/136624號
[專利文獻2]日本專利特開2017-014607號公報
[專利文獻3]日本專利特開2004-238666號公報
[專利文獻4]日本專利特開2004-277854號公報
但是，例如使用習知蝕刻液組成物，對分別由銅層、鎳層、及鉻層所形成之基體施行蝕刻時，有藉蝕刻所形成之細線的窄化幅度變大、直線性降低、出現蛇行之情形。又，例如使用習知蝕刻液組成物，欲對由銅層、鎳層、及鉻層所構成積層體統括施行蝕刻時，大多無法統括蝕刻。此情況，假設即使可統括蝕刻，但所形成細線的直線性低、細線出現蛇行、或細線出現所謂「鼠囓」(mouse bite)的較大缺損(長度3μm以上的缺損)。
緣是，本發明在於提供：即使統括對含有銅系層、與含鎳及鉻中至少其中一者之金屬系層的積層體施行蝕刻的情況，仍可形成窄化幅度少、直線性佳、且抑制發生較大缺損之細線，用於對含有銅、鎳、及鉻中至少1種之層施行蝕刻用的蝕刻液組成物。又，本發明在於提供：使用上述蝕刻液組成物的蝕刻方法。
本發明者等經深入鑽研，結果發現藉由依特定範圍量含有特定成分的蝕刻液組成物，即使統括對上述積層體施行蝕刻的情況，因蝕刻造成的窄化幅度少、能獲得直線性佳的細線，遂完成本發明。
即，本發明所提供的蝕刻液組成物，係用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層，施行蝕刻的蝕刻液組成物；含有：(A)鐵(III)離子0.1~10質量%；(B)氯化物離子0.1~10質量%；(C)甲酸離子0.01~5質量%；(D)從下述一般式(1)所示化合物與碳原子數1~4之直鏈或分支狀醇所構成群組中選擇至少1種化合物0.01~10質量%；(E)從下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、及由二元以上羧酸化合物施行脫水的單酐與二酐所構成群組中選擇至少1種化合物0.01~10質量%；以及水。
(上述一般式(1)中，R1與R3係表示各自獨立的氫原子、或碳原子數1~4之直鏈或分支狀烷基；R2係表示碳原子數1~4之直鏈或分支狀伸烷基；n係表示1~3之數值。)
(上述一般式(2)中，R4係表示碳原子數2~6之伸烷基；X1、X2及X3係表示下述一般式(3)所示基；X4係表示氫原子、或下述一般式(3)所示基；z係表示1~5之數值。)
(上述一般式(3)中、R5與R6係表示伸乙基或伸丙基；當R5為伸乙基時，R6為伸丙基；當R5為伸丙基的情況，R6為伸乙基；p與q係表示上述一般式(2)所示化合物之數量平均分子量為200~30,000、且環氧乙烷基含有量成為10~80質量%的數值；*係表示鍵結手。環氧乙烷與環氧丙烷的加成形態可為無規狀與嵌段狀之任一種。)
再者，本發明所提供的蝕刻方法，係包括使用上述蝕刻液組成物，對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層施行蝕刻的步驟。
根據本發明可提供即使統括對含有銅系層、以及鎳與鉻中至少其中一者之金屬系層的積層體施行蝕刻時，仍可形成窄化幅度少、直線性佳、且抑制了較大缺損發生的細線，用於對含有銅、鎳、及鉻中至少1種之層施行蝕刻用的蝕刻液組成物。又，根據本發明可提供使用上述蝕刻液組成物的蝕刻方法。
以下，針對本發明實施形態進行具體說明。本發明一實施形態的蝕刻液組成物(以下亦簡稱「蝕刻液組成物」)，係用於對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬的層(以下亦稱「被蝕刻材」)施行蝕刻者。該蝕刻液組成物係分別依後述特定濃度含有後述(A)~(E)成分，且含有水。所以，利用該蝕刻液組成物，即使對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體施行統括蝕刻時，仍可形成窄化幅度少、具有所需寬度的細線。又，此時可形成直線性佳、且抑制了較大缺損發生的細線。
本說明書中所謂「蝕刻」係指利用化學藥物等腐蝕作用的塑形或表面加工技法。蝕刻液組成物的具體用途係可舉例如：除去劑、表面平滑化劑、表面粗化劑、圖案形成用藥劑、基體上微量附著成分的洗淨液等。蝕刻液組成物因為對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬之層的除去速度快速，因而適合用作為除去劑。又，若使用於具三次元構造之微細形狀圖案的形成，可獲得矩 形等所需形狀的圖案，因而亦適合用作為圖案形成用藥劑。
本說明書的「銅系層」係包含銅(純銅)層、及以銅為主成分的合金(銅合金)層之總稱。銅合金層係含有銅50質量%以上(較佳60質量%以上)的合金層。銅合金層係可含有例如：鋅、鉛、錫、鐵、鋁、鎳、鉻、及錳等中之1或2以上的銅以外金屬。
本說明書所謂「含有鎳與鉻中至少其中一者的金屬系層」，若為上述銅系層以外的金屬層，且含有鎳與鉻中之至少其中一者，其餘並無特別的限定。該金屬系層係可舉例如：鎳層、鉻層、以及含有鎳與鉻中之至少其中一者的合金層等。該合金層中可含的鎳與鉻以外之金屬，係可舉例如：銅、鐵、銀、白金、金、鋁、鈦、鉬、鈷、鎢、及鈀等。
蝕刻液組成物係含有(A)鐵(III)離子(以下亦稱「(A)成分」)。藉由蝕刻液組成物中使用能供應(生成)鐵(III)離子的化合物，可使蝕刻液組成物含有鐵(III)離子。可對蝕刻液組成物中供應鐵(III)離子的化合物係可舉例如：氯化鐵(III)、溴化鐵(III)、碘化鐵(III)、硫酸鐵(III)、硝酸鐵(III)、及醋酸鐵(III)等。該等化合物係可為無水物、亦可為水合物。又，可對蝕刻液組成物中供應鐵(III)離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(A)成分的化合物中，較佳係使用氯化鐵(III)。
蝕刻液組成物中的(A)成分(鐵(III)離子)濃度(含有量)係0.1~10 質量%。若(A)成分的濃度未滿0.1質量%，無法獲得充分的蝕刻速度。另一方面，若(A)成分的濃度超過10質量%，則導致蝕刻速度變快，難以控制蝕刻速度。(A)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(A)成分的濃度較佳係0.2~5質量%、更佳係0.5~3質量%。
蝕刻液組成物係含有(B)氯化物離子(以下亦稱「(B)成分」)。藉由蝕刻液組成物中使用可供應(生成)氯化物離子的化合物，可使蝕刻液組成物含有氯化物離子。可對蝕刻液組成物中供應氯化物離子的化合物，係可舉例如：氯化鐵(III)、氯化氫、氯化銨、氯化鈉、氯化鉀、及氯化鋰等。可對蝕刻液組成物中供應氯化物離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(B)成分的化合物中，較佳係使用氯化鐵(III)、氯化氫，更佳係組合使用氯化鐵(III)與氯化氫。
蝕刻液組成物中的(B)成分(氯化物離子)濃度(含有量)係0.1~10質量%。若(B)成分濃度未滿0.1質量%，則蝕刻速度變為過慢，生產性降低。另一方面，若(B)成分的濃度超過10質量%，則蝕刻速度變為過快，會有較難控制蝕刻速度、或使被蝕刻材周邊構件、光阻等劣化的情況。(B)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(B)成分的濃度較佳係0.2~8質量%、更佳係0.5~5質量%。
蝕刻液組成物係含有(C)甲酸離子(以下亦稱「(C)成分」)。藉 由蝕刻液組成物中使用可供應(生成)甲酸離子的化合物，可使蝕刻液組成物含有甲酸離子。可對蝕刻液組成物供應甲酸離子的化合物係可舉例如：甲酸、甲酸鈉、甲酸鎂、甲酸鉀、甲酸鈣、甲酸錳、甲酸鈷、甲酸鎳、甲酸銅、甲酸鋅、甲酸鍶、甲酸鎘、及甲酸鋇等。可對蝕刻液組成物中供應甲酸離子的化合物係可單獨使用1種、亦可併用2種以上。可供應(C)成分的化合物中，較佳係使用甲酸。
蝕刻液組成物中的(C)成分(甲酸離子)濃度(含有量)係0.01~5質量%。若(C)成分的濃度未滿0.01質量%，則蝕刻速度變為過慢，生產性降低。另一方面，若(C)成分的濃度超過5質量%，則蝕刻速度過快，有難以控制蝕刻速度的情況。(C)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(C)成分的濃度較佳係0.05~3質量%、更佳係0.1~2質量%。
蝕刻液組成物係含有從(D)下述一般式(1)所示化合物、及碳原子數1~4之直鏈或分支狀醇所構成群組中選擇至少1種化合物(以下亦稱「(D)成分」)。
一般式(1)中，R1與R3係表示各自獨立的氫原子、或碳原子數1~4之直鏈或分支狀烷基。R2係表示碳原子數1~4之直鏈或分支狀伸烷基。n係表示1~3之數值。
一般式(1)中，R1與R3所示碳原子數1~4之直鏈或分支狀烷基，係可舉例如：甲基、乙基、正丙基、異丙基、正丁基、第二丁基、第三丁基、及異丁基等。R1與R3較佳係氫原子、甲基、乙基、丙基、正丁基。
一般式(1)中，R2所示碳原子數1~4之直鏈或分支狀伸烷基係可舉例如：亞甲基、伸乙基、伸正丙基、異伸丙基、伸正丁基、伸第二丁基、伸第三丁基、及伸異丁基等。R2較佳係伸丙基或異伸丙基、更佳係異伸丙基。
能使用為(D)成分的一般式(1)所示化合物係可舉例如：乙二醇單甲醚、二乙二醇單甲醚、三乙二醇單甲醚、乙二醇單異丙醚、二乙二醇單異丙醚、乙二醇單丁醚、二乙二醇單丁醚、三乙二醇單丁醚、乙二醇單異丁醚、二乙二醇單異丁醚、丙二醇單甲醚、二丙二醇單甲醚、三丙二醇單甲醚、丙二醇單丙醚、二丙二醇單丙醚、丙二醇單丁醚、二丙二醇單丁醚、三丙二醇單丁醚、乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二乙二醇甲基乙醚、二乙二醇二乙醚、二乙二醇二丁醚、及二丙二醇二甲醚等二醇醚類。
再者，能使用為(D)成分的碳原子數1~4之直鏈或分支狀醇，係可舉例如：甲醇、乙醇、丙醇、異丙醇、丁醇、2-丁醇、異丁醇、及第三丁醇等醇類。
上述一般式(1)所示化合物較佳係下述一般式(1-A)所示化合物。下述一般式(1-A)中的R1、R3、及n分別係與一般式(1)中的R1、R3、及n同義。
若(D)成分係使用上述一般式(1-A)所示化合物、及碳原子數3或4之分支狀醇中至少其中一者，則藉由使用蝕刻液組成物施行的蝕刻，可輕易形成窄化幅度小、且直線性佳的細線，故屬較佳。又，當使用二丙二醇單甲醚與異丙醇中至少其中一者的情況，可更加提高上述效果故屬更佳，特佳係二丙二醇單甲醚。
蝕刻液組成物中的(D)成分濃度(含有量)係0.01~10質量%。若(D)成分的濃度未滿0.01質量%，無法顯現出(D)成分的摻合效果。另一方面，即使(D)成分的濃度超過10質量%，但(D)成分的摻合效果並無法獲得進一步的提升。(D)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(D)成分的濃度較佳係0.05~8質量%、更佳係0.1~5質量%。
蝕刻液組成物係含有從(E)下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、以及由二元以上羧酸化合物進行脫水而形成的單酐及二酐所構成群組中選擇至少1種化合物(以下亦稱「(E)成分」)。
一般式(2)中，R4係表示碳原子數2~6之伸烷基；z係表示1~5之數值。X1、X2及X3係表示下述一般式(3)所示基；X4係表示氫原子、或下述一般式(3)所示基。
一般式(3)中，R5與R6係表示伸乙基或伸丙基；若R5為伸乙基的情況，R6為伸丙基；R5為伸丙基的情況，R6為伸乙基。p與q係表示使一般式(2)所示化合物成為數量平均分子量為200~30,000、且環氧乙烷基含有量成為10~80質量%的數值；*係表示鍵結手。環氧乙烷與環氧丙烷的加成形態為無規狀或嵌段狀之任一種。
一般式(2)中，R4所示碳原子數2~6之伸烷基係可舉例如：伸乙基、伸丙基、伸丁基、伸戊基、及伸己基等。該等基可鍵結於任何位置，亦可為分支。R5或R6所示伸丙基可為-CY1H-CY2H-(Y1及Y2係表示其中一者為氫原子、另一者為甲基)，亦可為-CH2-CH2-CH2-。一般式(2)所示化合物中，R4為伸乙基、z為1、X1~X4為一般式(3)所示基的多元醇，取得較為容易。上述一般式(2) 所示化合物的數量平均分子量係200~30,000，從蝕刻速度的觀點而言，較佳係200~7,500。又，上述一般式(2)所示化合物的環氧乙烷基含有量係10~80質量%，從蝕刻速度的觀點而言，較佳係10~50質量%。
能使用為(E)成分的膦酸化合物及其鹽，最好使用例如：羥亞乙基二膦酸、次氮基三亞甲基參(膦酸)、2-膦醯基丁烷-1,2,4-三羧酸、伸乙二胺四(亞甲膦酸)、二伸乙三胺五亞甲膦酸、及該等的鹼金屬(較佳係鈉)鹽等。
能使用為(E)成分的胺基羧酸化合物及其鹽之較佳具體例，係可舉例如：天冬醯胺、絲胺酸、天冬胺酸、谷胺酸、麩胺酸、蘇胺酸、精胺酸、組胺酸、溶胞素、酪胺酸、及半胱氨酸等胺基酸；以及該等的鹼金屬(較佳係鈉)鹽等。胺基羧酸化合物及其鹽的更佳具體例，係可舉例如：伸乙二胺四醋酸、氮基三醋酸、二伸乙三胺五醋酸、N-(2-羥乙基)伸乙二胺三醋酸、三伸乙四胺六醋酸、1,3-伸丙二胺四醋酸、1,3-二胺基-2-羥丙烷四醋酸、2-羥乙基亞胺二醋酸、N,N-二(2-羥乙基)甘胺酸、二醇醚二胺四醋酸、N,N-二(羧甲基)麩胺酸、伸乙二胺二琥珀酸、四伸乙五胺七醋酸、及該等的鹼金屬(較佳係鈉)鹽等。該等之中，更佳係伸乙二胺四醋酸四鈉。
能使用為(E)成分的二元以上羧酸化合物及其鹽，係可舉例如：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、以及該等的無水物及鹼金 屬(較佳係鈉)鹽等。
能使用為(E)成分之由二元以上羧酸化合物施行脫水而形成的單酐與二酐，係可例如：藉由使上述二元以上羧酸化合物施行脫水縮合而獲得的化合物。
上述(E)成分係可從該等之中單獨使用1種、亦可併用2種以上。較佳係併用2種以上(E)成分，其中更佳係組合使用一般式(2)所示化合物、與胺基羧酸化合物或其鹽。藉由使用此種組合的(E)成分，當對含有銅系層、與含鎳與鉻中至少其中一者之金屬系層的積層體施行統括蝕刻時，能更加提高可形成直線性佳、不易發生較大缺損之細線的效果。
蝕刻液組成物中的(E)成分濃度(含有量)係0.01~10質量%。若(E)成分的濃度未滿0.01質量%，無法顯現出(E)成分的摻合效果。另一方面，即使(E)成分的濃度超過10質量%，但(E)成分的摻合效果並無法獲得進一步提升。(E)成分的濃度係依照被蝕刻材的厚度與寬度，可在上述濃度範圍內適當調整。(E)成分的濃度較佳係0.05~8質量%、更佳係0.1~5質量%。
蝕刻液組成物係更進一步含有水。蝕刻液組成物中可將水使用為溶劑，將蝕刻液組成物作成水溶液的形態。蝕刻液組成物中的水含有量最好配合前述(A)~(E)成分的濃度，將其餘部分設為水。使用後述添加劑的情況，較佳係配合(A)~(E)成分、及添加劑的濃度，其 餘部分使用水。蝕刻液組成物中的水濃度(含有量)較佳係55~99質量%左右。
再者，在蝕刻液組成物中，除前述(A)~(E)成分之外，於不致妨礙本發明效果之範圍內，亦可含有周知添加劑。添加劑係可舉例如：還原劑、蝕刻液組成物的安定化劑、各成分的可溶化劑、消泡劑、比重調節劑、黏度調節劑、潤濕性改善劑、及氧化劑等。使用該等添加劑時，蝕刻液組成物中的添加劑濃度(含有量)一般分別可設為0.001~40質量%範圍。
再者，蝕刻液組成物中，除前述(A)~(E)成分之外，在不致妨礙本發明效果之範圍內，亦可含有配合蝕刻液組成物用途的周知任意成分。任意成分係可舉例如：界面活性劑、有機酸、唑類化合物、嘧啶類化合物、硫脲類化合物、胺類化合物、烷基吡咯啶酮類化合物、聚丙烯醯胺類化合物、過氧化氫、及過硫酸鹽等。使用該等任意成分時，蝕刻液組成物中的任意成分濃度(含有量)一般分別可設為0.001質量%~10質量%範圍。當蝕刻液組成物含有上述添加劑與任意成分的情況，蝕刻液組成物中的添加劑與任意成分之合計濃度(含有量)，最好設為0.001~40質量%範圍。
界面活性劑係可舉例如：氟化烷基甜菜
、及氟化烷基聚氧乙烯醚等氟系兩性界面活性劑。
有機酸係可舉例如：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、羥三甲基乙酸、乙醯丙酸(levulinic acid)、及β-氯丙酸等。
唑類化合物係可舉例如：咪唑、2-甲基咪唑、2-十一烷基-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、2-十一烷基苯并咪唑、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；以及苯并噻唑、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。
嘧啶類化合物係可舉例如：二胺基嘧啶、三胺基嘧啶、四胺基嘧啶、及巰基嘧啶等。
硫脲類化合物係可舉例如：硫脲、乙烯硫脲、硫二甘醇(thiodiglycol)、及硫醇等。
胺類化合物係可舉例如：二戊胺、二丁基胺、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、及該等之鹽酸鹽等等。
烷基吡咯啶酮類化合物係可舉例如：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。
聚丙烯醯胺類化合物係可舉例如：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。
本發明一實施形態的蝕刻方法係包括有：使用上述蝕刻液組成物，對含有從銅、鎳、及鉻所構成群組中選擇至少1種金屬的層施行蝕刻之步驟。該蝕刻方法所使用的蝕刻液組成物係如上述，可對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體，統括施行蝕刻。所以，該蝕刻方法更佳係適用於對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體，統括施行蝕刻的情況。特佳係該蝕刻方法係適用於對含有銅(Cu)層、與含有鎳(Ni)層與鉻(Cr)層中至少其中一者之金屬系層的積層體，統括施行蝕刻的情況。
積層體的銅系層與金屬系層分別可為1層、亦可為2層以上。又，積層體的銅系層與金屬系層之配置關係並無特別的限定，金屬系層係可配置於銅系層的上層、亦可配置於下層、亦可上層與下層均有配置。又，銅系層與金屬系層亦可交替積層。
具體的蝕刻方法並無特別的限定，可採用一般的蝕刻方法。例如可利用浸漬式、噴霧式、及旋轉式等進行的蝕刻方法。又，亦可依照批次式、流動式、以及利用蝕刻劑的氧化還原電位、比重、或酸濃度進行之自動控制式等一般方式使用蝕刻液組成物。
例如利用浸漬式蝕刻方法，對在矽基板、玻璃基板等基體上，形成有由Cu層、Ni層、及Cr層所構成積層體的基材施行蝕刻時，將該基材依適當蝕刻條件浸漬於蝕刻液組成物中之後，經上拉，則可統括地對基體上的Cu層、Ni層、及Cr層施行蝕刻。
浸漬式蝕刻方法的蝕刻條件並無特別的限定，可配合被蝕刻材的形狀、膜厚等任意設定。例如蝕刻溫度較佳係10~60℃、更佳係20~40℃。因為蝕刻液組成物的溫度將因反應熱而上升，因而視需要為了使蝕刻液組成物的溫度能維持於上述範圍內，亦可利用公知手段進行溫度控制。又，蝕刻時間係只要設定為被蝕刻材能被完全蝕刻的充分必要時間即可，並無特別的限定。例如若為膜厚10~1000nm左右的被蝕刻材，只要依上述溫度範圍施行1分鐘~24小時左右的蝕刻即可。
例如利用噴霧式蝕刻方法，對在矽基板、玻璃基板等基體上，形成有由Cu層、Ni層、及Cr層所構成積層體的基材施行蝕刻時，藉由將蝕刻液組成物依適當條件朝該基材施行噴霧，可統括地對基體上的Cu層、Ni層、及Cr層施行蝕刻。
噴霧式蝕刻方法的蝕刻條件並無特別的限定，可配合被蝕刻材的形狀、膜厚等任意設定。例如噴霧條件係可從0.01~1.0MPa範圍內選擇，較佳係0.03~0.2MPa範圍、更佳係0.05~0.15MPa範圍。又，當使用蝕刻液組成物利用噴霧式形成細線的情況，在噴霧壓0.05~0.15MPa時，可獲得細線上寬與下寬差非常小的細線，故特佳。又，蝕刻溫度較佳係10~60℃、更佳係20~40℃。因為蝕刻液組成物的溫度將因反應熱而上升，因而視需要為了使蝕刻液組成物的溫度能維持於上述範圍內，亦可利用公知手段進行溫度控制。又，蝕刻時間係只要設定為被蝕刻材能被完全蝕刻的充分必要時間即可，並無特別的限定。例如若為膜厚800nm左右的被蝕刻材，只要依上述溫度範圍施行60~600秒左右的蝕刻即可。
本發明一實施形態的蝕刻方法，為了使因重複進行蝕刻而劣化的蝕刻液組成物復原，亦可更進一步設有對蝕刻液組成物添加補充液的步驟。例如上述自動控制式蝕刻方法的情況，若預先在蝕刻裝置中安裝補充液，可對蝕刻液組成物添加補充液。補充液係可使用例如：(A)成分、(B)成分、及(C)成分中之至少任一成分的水溶液；以及(D)成分的水溶液等。該等水溶液(補充液)中的各成分濃度係例 如設為蝕刻液組成物中各成分濃度的3~20倍左右即可。又，在補充液中視需要亦可添加含有蝕刻液組成物必要成分、或任意成分的前述各成分。
上述蝕刻液組成物、及使用其的蝕刻方法，係當形成微細圖案電路佈線時可提供精密蝕刻。所以，上述蝕刻液組成物及蝕刻方法係除印刷電路板之外，尚可使用於要求超細間距的封裝用基板、COF(chip on film,chip on flexible，薄膜覆晶)、及TAB(tape automated bonding，捲帶式自動接著)用途之移除法、半加成法。
以下，利用實施例與比較例，針對本發明進行更詳細說明，惟本發明並不因該等而受限定。
將表1所示化合物及水，依蝕刻液組成物中的(A)~(E)成分成為表2所示濃度方式進行混合，獲得實施例1~5的蝕刻液組成物。另外，依所摻合化合物與水的合計成為100質量%方式摻合水。(A)成分(鐵(III)離子)的濃度係利用氯化鐵(III)進行調整，(B)成分(氯化物離子)的濃度係利用氯化鐵(III)與氯化氫進行調整。(E)成分係使用下示「E-1」、「E-2」、及「E-3」。
E-1：伸乙二胺四醋酸四鈉
E-2：ADEKA公司製商品名「Adeka PullulonicTR-702」[由環 氧丙烷及環氧乙烷嵌段加成於伸乙二胺之活性氫上的化合物(數量平均分子量3500、環氧乙烷含有量20質量%，一般式(2)中，R4=伸乙基、z=1、R5=伸丙基、R6=伸乙基、X4≠氫原子)]
E-3：ADEKA公司製商品名「Adeka PullulonicTR-704」[由環氧丙烷及環氧乙烷嵌段加成於伸乙二胺之活性氫上的化合物(數量平均分子量5000、環氧乙烷含有量40質量%、一般式(2)中，R4=伸乙基、z=1、R5=伸丙基、R6=伸乙基、X4≠氫原子)]
將表3所示化合物及水，依蝕刻液組成物中的(A)~(E)成分成為表4所示濃度方式進行混合，獲得比較例1~3的蝕刻液組成物。另外，依所摻合化合物與水的合計成為100質量%方式摻合水。(A)成分(鐵(III)離子)的濃度係利用氯化鐵(III)進行調整，(B)成分(氯化物離子)的濃度係利用氯化鐵(III)與氯化氫進行調整。
對在玻璃基體上依序積層著：Cu層(厚度300nm)、Ni層(厚度 150nm)、及Cr層(厚度150nm)的基材。使用正型液狀光阻形成寬30μm、開口部30μm的光阻圖案。將已形成光阻圖案的基材裁剪為長20mm×寬20mm而獲得測試片。對所獲測試片，使用實施例1~5之蝕刻液組成物，依30℃、噴霧壓0.07MPa、180秒的條件，利用噴霧式施行圖案蝕刻，而製得屬於細線狀圖案的實施例圖案No.1~5。
對在玻璃基體上依序積層著：Cu層(厚度300nm)、Ni層(厚度150nm)、及Cr層(厚度150nm)的基材。使用正型液狀光阻形成寬30μm、開口部30μm的光阻圖案。將已形成光阻圖案的基材裁剪為長20mm×寬20mm而獲得測試片。對所獲測試片，使用比較例1~3之蝕刻液組成物，依30℃、噴霧壓0.07MPa、180秒的條件，利用噴霧式施行圖案蝕刻，而製得屬於細線狀圖案的比較例圖案No.1~3。
從圖案上方使用雷射顯微鏡進行觀察，確認屬於光阻開口部之部分的積層體(Cu層、Ni層、及Cr層之積層體)是否被完全除去。將已完全除去者評為「+」，將無法完全除去者評為「-」。又，亦針對所形成圖案的形狀進行評價。將發現圖案呈蛇行、或觀察到長度達3μm以上缺損者評為「-」，將圖案未出現蛇行、或未發現長度達3μm以上缺損者評為「+」。結果如表5所示。
由表5所示結果，確認到使用實施例1~5之蝕刻液組成物的實施例6~10，可乾淨除去光阻開口部之由Cu層、Ni層、及Cr層構成的積層體，能形成細線狀圖案。又，得知所獲得圖案的直線性佳、亦未發現缺損產生。另一方面，使用比較例1之蝕刻液組成物的比較例4，並無法除去光阻開口部之由Cu層、Ni層、及Cr層構成的積層體。又，使用比較例2與3之蝕刻液組成物的比較例5與6，確認到所獲得圖案的直線性低、且發生較大缺損。
Claims (5)
- 一種蝕刻液組成物，係用於對含有從銅、鎳及鉻所構成群組中選擇之至少1種金屬之層施行蝕刻的蝕刻液組成物；其含有：(A)鐵(III)離子0.1~10質量%；(B)氯化物離子0.1~10質量%；(C)甲酸離子0.01~5質量%；(D)從下述一般式(1)所示化合物與碳原子數1~4之直鏈或分支狀醇所構成群組中選擇之至少1種化合物0.01~10質量%；(E)從下述一般式(2)所示化合物、膦酸化合物及其鹽、胺基羧酸化合物及其鹽、二元以上羧酸化合物及其鹽、及由二元以上羧酸化合物施行脫水而成的單酐與二酐所構成群組中選擇之至少1種化合物0.01~10質量%；以及水；
- 如請求項1之蝕刻液組成物，其中，上述一般式(1)所示化合物係下述一般式(1-A)所示化合物：
- 如請求項1之蝕刻液組成物，其中，上述(D)成分係含有二丙二醇單甲醚與異丙醇中之至少其中一者。
- 如請求項1之蝕刻液組成物，其係用於統括對含有銅系層、及含有鎳與鉻中至少其中一者之金屬系層的積層體施行蝕刻。
- 一種蝕刻方法，係包括有：使用請求項1至4中任一項之蝕刻液組成物，對含有從銅、鎳及鉻所構成群組中選擇之至少1種金屬之層，施行蝕刻的步驟。
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