TWI510676B - Metal etchant compositions for etching copper and molybdenum and their use for etching Metal etching method for copper and molybdenum - Google Patents
Metal etchant compositions for etching copper and molybdenum and their use for etching Metal etching method for copper and molybdenum Download PDFInfo
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- TWI510676B TWI510676B TW102124702A TW102124702A TWI510676B TW I510676 B TWI510676 B TW I510676B TW 102124702 A TW102124702 A TW 102124702A TW 102124702 A TW102124702 A TW 102124702A TW I510676 B TWI510676 B TW I510676B
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- 229910052751 metal Inorganic materials 0.000 title claims description 89
- 239000002184 metal Substances 0.000 title claims description 89
- 239000000203 mixture Substances 0.000 title claims description 44
- 238000005530 etching Methods 0.000 title claims description 33
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims description 29
- 229910052750 molybdenum Inorganic materials 0.000 title claims description 29
- 239000011733 molybdenum Substances 0.000 title claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 23
- 229910052802 copper Inorganic materials 0.000 title claims description 23
- 239000010949 copper Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 69
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000001384 succinic acid Substances 0.000 claims description 18
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-N E-Sorbic acid Chemical compound C\C=C\C=C\C(O)=O WSWCOQWTEOXDQX-MQQKCMAXSA-N 0.000 claims description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011087 fumaric acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 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 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 239000011976 maleic acid Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Description
本發明是有關於一種用於蝕刻銅與鉬的金屬蝕刻劑組成物，特別是指一種含有特定相對比例之丁二酸及乙酸的金屬蝕刻劑組成物。This invention relates to a metal etchant composition for etching copper and molybdenum, and more particularly to a metal etchant composition containing a specific relative proportion of succinic acid and acetic acid.
在液晶顯示器的製程中，通常會使用含有銅與鉬的多層金屬薄膜作為金屬層，且一般是透過溼式蝕刻使該金屬層產生預定圖樣。倘若該圖樣的金屬層端部與基板間存在底切現象(undercut)，將使得後續製程中的覆蓋不平整，進而導致非預期的斷路，因此金屬層端部與基板間的蝕刻形狀對於液晶顯示器的良率至關重要，而溼式蝕刻所使用的蝕刻劑組成即為控制蝕刻形狀的關鍵因素之一。In the process of a liquid crystal display, a multilayer metal film containing copper and molybdenum is generally used as a metal layer, and the metal layer is generally subjected to a predetermined pattern by wet etching. If there is an undercut between the end of the metal layer of the pattern and the substrate, the coverage in the subsequent process will be uneven, thereby causing an unexpected disconnection, so the etching shape between the end of the metal layer and the substrate is for the liquid crystal display. The yield is critical, and the etchant composition used in wet etching is one of the key factors controlling the shape of the etch.
中華民國專利公告第I231275號揭露一種用於一銅與鉬的多層的蝕刻溶液，包含特定含量比例的過氧化氫、有機酸、磷酸鹽、含氮添加物、氟化合物及水。然而，其需要特定含量比例的磷酸鹽及含氮添加物，才能得到具有良好配線形狀與均勻性的金屬層，並避免底切現象產生。The Republic of China Patent Publication No. I231275 discloses a multilayer etching solution for copper and molybdenum containing a specific proportion of hydrogen peroxide, an organic acid, a phosphate, a nitrogen-containing additive, a fluorine compound, and water. However, it requires a specific proportion of phosphate and nitrogen-containing additives to obtain a metal layer having good wiring shape and uniformity, and to avoid undercutting.
中華民國專利公開第201137176號揭露一種具有銅層及鉬層之多層薄膜用蝕刻液，包含過氧化氫、無機酸、有機酸、胺化合物、吡咯環類及過氧化氫安定劑。然而，其需要硝酸及胺化合物才能得到具有良好配線形狀與均勻性的金屬層，並避免底切現象產生。The Republic of China Patent Publication No. 201137176 discloses an etching solution for a multilayer film having a copper layer and a molybdenum layer, comprising hydrogen peroxide, an inorganic acid, an organic acid, an amine compound, a pyrrole ring, and a hydrogen peroxide stabilizer. However, it requires a nitric acid and an amine compound to obtain a metal layer having a good wiring shape and uniformity, and avoids undercutting.
因此，本發明之目的，即在提供一種用於蝕刻銅與鉬的金屬蝕刻劑組成物，能得到具有良好配線形狀與均勻性的金屬層並有效避免底切現象產生。Accordingly, it is an object of the present invention to provide a metal etchant composition for etching copper and molybdenum, which can provide a metal layer having a good wiring shape and uniformity and effectively avoid undercutting.
於是本發明用於蝕刻銅與鉬的金屬蝕刻劑組成物包含過氧化氫及一有機酸組分；該有機酸組分包括丁二酸及乙酸；其中，丁二酸與乙酸的重量比例範圍為1：1.2~1：3。Thus, the metal etchant composition for etching copper and molybdenum of the present invention comprises hydrogen peroxide and an organic acid component; the organic acid component comprises succinic acid and acetic acid; wherein the weight ratio of succinic acid to acetic acid is in the range of 1:1.2~1:3.
本發明之另一目的，即在提供一種用於蝕刻銅與鉬的金屬蝕刻方法，在對於一含有銅與鉬的多層金屬薄膜進行蝕刻時能得到良好的配線形狀與均勻性並有效避免底切現象產生。Another object of the present invention is to provide a metal etching method for etching copper and molybdenum, which can obtain good wiring shape and uniformity and effectively avoid undercutting when etching a multilayer metal film containing copper and molybdenum. The phenomenon occurs.
於是本發明用於蝕刻銅與鉬的金屬蝕刻方法包含將如上所述的金屬蝕刻劑組成物與一多層金屬薄膜接觸，使該多層金屬薄膜產生蝕刻，其中，該多層金屬薄膜包括一鉬層及一堆疊於該鉬層上的銅層。Thus, the metal etching method for etching copper and molybdenum according to the present invention comprises contacting the metal etchant composition as described above with a multilayer metal film to etch the multilayer metal film, wherein the multilayer metal film comprises a molybdenum layer And a copper layer stacked on the molybdenum layer.
本發明用於蝕刻銅與鉬的金屬蝕刻劑組成物之功效在於：其藉由包含特定相對比例之丁二酸及乙酸，在進行含有銅與鉬的多層金屬蝕刻時，能得到良好的配線形 狀與均勻性，並有效避免底切現象產生。The effect of the metal etchant composition for etching copper and molybdenum of the present invention is that it can obtain a good wiring shape when performing multilayer metal etching containing copper and molybdenum by containing a specific relative ratio of succinic acid and acetic acid. Shape and uniformity, and effectively avoid undercutting.
以下將就本發明內容進行詳細說明：申請人發現：在本發明用於蝕刻銅與鉬的金屬蝕刻劑組成物中，特定比例的丁二酸與乙酸可穩定過氧化氫，在進行多層金屬蝕刻時能使銅氧化物溶解並產生錯合物，亦有助於降低賈法尼電流(galvanic current)。The present invention will be described in detail below. Applicants have found that in the metal etchant composition for etching copper and molybdenum of the present invention, a specific ratio of succinic acid and acetic acid can stabilize hydrogen peroxide during multilayer metal etching. It can dissolve copper oxide and produce a complex compound, which also helps to reduce the galvanic current.
在該金屬蝕刻劑組成物中，當丁二酸與乙酸的重量比例高於1：1.2時，丁二酸的比例過高(乙酸的比例過低)，導致產生金屬氧化物與丁二酸結合，形成難溶化合物覆蓋於金屬表面，使得進行多層金屬蝕刻時，部分金屬表面覆蓋的難溶化合物阻止過氧化氫對於該部分進行蝕刻，致生不良的配線形狀與均勻性；當丁二酸與乙酸的重量比例低於1：3時，丁二酸的比例過低(乙酸的比例過高)，導致產生金屬氧化物與乙酸結合，形成難溶化合物覆蓋於金屬表面，使得進行多層金屬蝕刻時，部分金屬表面覆蓋的難溶化合物阻止過氧化氫對於該部分進行蝕刻，致生不良的配線形狀與均勻性。較佳地，在該金屬蝕刻劑組成物中，丁二酸與乙酸的重量比例範圍為1：1.5~1：2.67。In the metal etchant composition, when the weight ratio of succinic acid to acetic acid is higher than 1:1.2, the ratio of succinic acid is too high (the ratio of acetic acid is too low), resulting in the formation of metal oxide combined with succinic acid. Forming a poorly soluble compound covering the metal surface, so that when the multilayer metal etching is performed, a part of the metal surface covering the insoluble compound prevents the hydrogen peroxide from etching the portion, resulting in poor wiring shape and uniformity; when succinic acid and When the weight ratio of acetic acid is less than 1:3, the proportion of succinic acid is too low (the ratio of acetic acid is too high), resulting in the formation of a metal oxide combined with acetic acid, forming a poorly soluble compound covering the metal surface, so that when performing multilayer metal etching The insoluble compound covered by part of the metal surface prevents the hydrogen peroxide from etching the portion, resulting in poor wiring shape and uniformity. Preferably, the weight ratio of succinic acid to acetic acid in the metal etchant composition ranges from 1:1.5 to 1:2.67.
較佳地，以該金屬蝕刻劑組成物的總重為100 wt%，乙酸的含量範圍為2~8 wt%。Preferably, the total weight of the metal etchant composition is 100 wt%, and the acetic acid content ranges from 2 to 8 wt%.
較佳地，該有機酸組分還包括至少一種由下列群組所組成的有機酸：乙醇酸、檸檬酸、甲酸、乙二酸、乙醛酸、丙酸、丙烯酸、丙酮酸、2-羥基丙酸、丁酸、2-甲基丙酸、3-丁酮酸、反-丁烯二酸、順-丁烯二酸、丁酮二酸 、2,3-二羥基丁二酸、反-2-丁烯酸、戊酸、戊二酸、己酸、己二酸、反，反-2,4-己二烯酸、庚酸、庚二酸、苯甲酸、鄰羥基苯甲酸、辛酸及其組合。更佳地，該該有機酸是選自於乙醇酸或檸檬酸。Preferably, the organic acid component further comprises at least one organic acid consisting of glycolic acid, citric acid, formic acid, oxalic acid, glyoxylic acid, propionic acid, acrylic acid, pyruvic acid, 2-hydroxyl Propionic acid, butyric acid, 2-methylpropionic acid, 3-butanone acid, trans-butenedioic acid, cis-butenedioic acid, butanone diacid , 2,3-dihydroxysuccinic acid, trans-2-butenoic acid, valeric acid, glutaric acid, caproic acid, adipic acid, trans, trans-2,4-hexadienoic acid, heptanoic acid, pimelic acid, Benzoic acid, o-hydroxybenzoic acid, octanoic acid, and combinations thereof. More preferably, the organic acid is selected from the group consisting of glycolic acid or citric acid.
在該金屬蝕刻劑組成物中，過氧化氫是作為氧化劑，較佳地，以該金屬蝕刻劑組成物的總重為100 wt%，過氧化氫的含量範圍為2~7 wt%。In the metal etchant composition, hydrogen peroxide is used as the oxidizing agent, preferably, the total weight of the metal etchant composition is 100 wt%, and the hydrogen peroxide content is in the range of 2 to 7 wt%.
較佳地，該金屬蝕刻劑組成物的pH值為3.0~4.5。若該金屬蝕刻劑組成物的pH值大於4.5，將造成過氧化氫安定性下降，使蝕刻表現不穩定與蝕刻液安定性不足的現象；若該金屬蝕刻劑組成物的pH值小於3.0，將造成鉬層被氧化後形成之氧化物難以溶解。在本發明之具體實施例中，該金屬蝕刻劑組成物的pH值為3.5。Preferably, the metal etchant composition has a pH of from 3.0 to 4.5. If the pH of the metal etchant composition is greater than 4.5, the stability of hydrogen peroxide is lowered, the etching performance is unstable, and the stability of the etching solution is insufficient; if the pH of the metal etchant composition is less than 3.0, The oxide formed by the oxidation of the molybdenum layer is difficult to dissolve. In a particular embodiment of the invention, the metal etchant composition has a pH of 3.5.
本發明之其他的特徵及功效，將於參照圖式的實施方式中清楚地呈現，其中：圖1是一SEM照片，說明應用例2之雙層金屬薄膜的截面；及圖2是一SEM照片，說明比較應用例1之雙層金屬薄膜的截面。Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a SEM photograph illustrating a cross section of a two-layer metal film of Application Example 2; and FIG. 2 is an SEM photograph. A cross section of the two-layer metal film of Comparative Example 1 will be described.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
<實施例><Example>
[實施例1~3]金屬蝕刻劑組成物E1~E3[Examples 1 to 3] Metal etchant compositions E1 to E3
分別將過氧化氫、丁二酸、乙酸、乙醇酸、檸檬酸與水以下表1所示之比例均勻混合，並以氫氧化鈉調整混合液的pH值至3.5，分別得到實施例1~3的金屬蝕刻劑組成物E1 ~E3 。Hydrogen peroxide, succinic acid, acetic acid, glycolic acid, citric acid and water were uniformly mixed in the ratio shown in Table 1 below, and the pH of the mixture was adjusted to 3.5 with sodium hydroxide to obtain Examples 1 to 3, respectively. Metal etchant composition E1 ~ E3 .
[比較例1~6]金屬蝕刻劑組成物CE1~CE6[Comparative Examples 1 to 6] Metal etchant compositions CE1 to CE6
分別將過氧化氫、乙酸、乙醇酸、檸檬酸與水以下表1所示之比例均勻混合，並以氫氧化鈉調整比較例1之混合液的pH值至3.5，調整比較例2~6之混合液的pH值至4，分別得到比較例1~6的金屬蝕刻劑組成物CE1 ~CE6 。Hydrogen peroxide, acetic acid, glycolic acid, citric acid and water were uniformly mixed in the ratio shown in Table 1 below, and the pH of the mixed solution of Comparative Example 1 was adjusted to 3.5 with sodium hydroxide to adjust Comparative Examples 2 to 6. The pH of the mixed solution was adjusted to 4, and the metal etchant compositions CE1 to CE6 of Comparative Examples 1 to 6 were obtained, respectively.
[比較例7]金屬蝕刻劑組成物CE7[Comparative Example 7] Metal etchant composition CE7
比較例7的金屬蝕刻劑組成物CE7 與中華民國專利公開第201137176號中比較例1的蝕刻液相同，其部分主要成分含量比例如下表1所示。The metal etchant composition CE7 of Comparative Example 7 is the same as the etching liquid of Comparative Example 1 of the Republic of China Patent Publication No. 201137176, and the content ratio of some of the main components is as shown in Table 1 below.
「--」表示未添加；「-」表示未添加丁二酸或未添加乙酸。"--" means no addition; "-" means no succinic acid added or no acetic acid added.
<應用例>雙層金屬薄膜蝕刻<Application Example> Double-layer metal film etching
[應用例1~3及比較應用例1~6][Application Examples 1 to 3 and Comparative Application Examples 1 to 6]
在一玻璃基板上濺鍍鉬以形成一鉬隔絕層，再於該鉬隔絕層上濺鍍銅以形成一銅導體層，再於該銅導體層上塗佈形成一光阻層，藉此得到一雙層金屬薄膜(鉬層厚度為180 nm，銅層厚度為550 nm)。依此步驟分別製得應用例1~3及比較應用例1~6的雙層金屬薄膜。Molybdenum is sputtered on a glass substrate to form a molybdenum insulating layer, copper is sputtered on the molybdenum insulating layer to form a copper conductor layer, and a photoresist layer is formed on the copper conductor layer to obtain a photoresist layer. A two-layer metal film (the thickness of the molybdenum layer is 180 nm and the thickness of the copper layer is 550 nm). According to this step, the double-layer metal films of Application Examples 1 to 3 and Comparative Application Examples 1 to 6 were respectively obtained.
將上述實施例1~3及比較例1~6的金屬蝕刻劑組成物E1 ~E3 及CE1 ~CE6 維持在34~35℃，分別將上述雙層金屬薄膜浸入該等金屬蝕刻劑組成物中蝕刻45~60秒，分別得到應用例1~3及比較應用例1~6的經蝕刻之雙層金屬薄膜A1 ~A3 及B1 ~B6 。以目視或光學顯微鏡分別觀察A1 ~A3 及B1 ~B6 的配線形狀與均勻性，並分別以掃描式電子顯微鏡(SEM)觀察A1 ~A3 及B1 ~B4 的截面，並測量鉬層與玻璃基板的接觸角，判定其是否存在有底 切現象(接觸角大於90度)，結果如下表2所示。其中，應用例2及比較應用例1的SEM照片分別如圖1及圖2所示。The metal etchant compositions E1 to E3 and CE1 to CE6 of the above Examples 1 to 3 and Comparative Examples 1 to 6 were maintained at 34 to 35 ° C, and the double-layered metal film was immersed in the metal etchant composition, respectively. 45 to 60 seconds, the etched double-layer metal films A1 to A3 and B1 to B6 of Application Examples 1 to 3 and Comparative Application Examples 1 to 6 were respectively obtained. The wire shape and uniformity of A1 ~ A3 and B1 ~ B6 were observed by visual or optical microscope, and the cross sections of A1 ~ A3 and B1 ~ B4 were observed by scanning electron microscope (SEM), and the molybdenum layer and the glass substrate were measured. The contact angle was judged whether or not there was an undercut (contact angle greater than 90 degrees), and the results are shown in Table 2 below. The SEM photographs of Application Example 2 and Comparative Application Example 1 are shown in FIGS. 1 and 2, respectively.
[比較應用例7][Comparative Application Example 7]
比較應用例7的雙層金屬薄膜B7 與中華民國專利公開第201137176號中比較例1的蝕刻後之多層薄膜試料相同，且該專利揭示其存在有底切現象。The double-layered metal film B7 of Comparative Example 7 is the same as the etched multilayer film sample of Comparative Example 1 of the Republic of China Patent Publication No. 201137176, and the patent discloses that there is an undercut phenomenon.
＊ 「×」表示在雙層金屬薄膜的蝕刻表面有未被光阻覆蓋之金屬薄膜殘留造成配線形狀與與預定義之形狀不相同；「○」表示無金屬薄膜殘留且配線形狀與與預定義之形狀相同。 * "X" indicates that the metal film remaining on the etched surface of the double-layered metal film is not covered by the photoresist, and the wiring shape is different from the predefined shape; "○" means no metal film remains and the wiring shape and the predefined shape the same.
＊＊ 在雙層金屬薄膜的截面中，若鉬層與玻璃基板的接觸角大於90度表示存在有底切現象；若鉬層與玻璃基板的接觸角小於或等於90度表示無底切現象。 ** In the cross section of the double-layer metal film, if the contact angle of the molybdenum layer with the glass substrate is greater than 90 degrees, there is an undercut phenomenon; if the contact angle of the molybdenum layer with the glass substrate is less than or equal to 90 degrees, there is no undercut phenomenon.
由表2結果可以得知：經由金屬蝕刻劑組成物E1 ~E3 蝕刻得到的雙層金屬薄膜A1 ~A3 皆無觀察到底切現象，而經由金屬蝕刻劑組成物CE1 ~CE4 及CE7 蝕刻得到的雙層金屬薄膜B1 ~B4 及B7 皆有觀察到明顯的底切現象，顯示包含丁二酸及乙酸的金屬蝕刻劑組成物E1 ~E3 能有效避免進行金屬蝕刻時產生底切現象，而不含有丁二酸的金屬蝕刻劑組成物CE1 ~CE4 與不含有乙酸的金屬蝕刻劑組成物CE4 及CE7 皆無法有效防止底切現象產生。It can be seen from the results in Table 2 that the double-layered metal films A1 to A3 etched through the metal etchant compositions E1 to E3 have no observation of the undercut phenomenon, and the double layer etched through the metal etchant compositions CE1 to CE4 and CE7 . Metal film B1 ~ B4 and B7 have observed obvious undercut phenomenon, indicating that the metal etchant compositions E1 ~ E3 containing succinic acid and acetic acid can effectively avoid undercutting during metal etching, and do not contain Ding The acid metal etchant compositions CE1 to CE4 and the metal etchant compositions CE4 and CE7 which do not contain acetic acid are not effective in preventing undercutting.
此外，經由金屬蝕刻劑組成物CE5 及CE6 蝕刻得到的雙層金屬薄膜B5 及B6 ，由於CE5 及CE6 中的丁二酸與乙酸的重量比例過低或過高，因此在雙層金屬薄膜的蝕刻表面有未被光阻覆蓋之金屬薄膜殘留，造成配線形狀與預定義之形狀不相同。In addition, the two-layer metal films B5 and B6 etched through the metal etchant compositions CE5 and CE6 are etched in the double-layer metal film because the weight ratio of succinic acid to acetic acid in CE5 and CE6 is too low or too high. The surface of the metal film that is not covered by the photoresist remains, causing the wiring shape to be different from the predefined shape.
綜上所述，本發明用於蝕刻銅與鉬的金屬蝕刻劑組成物藉由包含特定相對比例之丁二酸及乙酸，在進行多層金屬蝕刻時有助於降低賈法尼電流，能得到具有良好配線形狀與均勻性的金屬層，並有效避免底切現象產生，故確實能達成本發明之目的。In summary, the metal etchant composition for etching copper and molybdenum of the present invention helps to reduce the japanidal current during multilayer metal etching by containing a specific relative ratio of succinic acid and acetic acid, and A metal layer having a good wiring shape and uniformity and an undercut phenomenon are effectively prevented, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
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