TWI405874B - 具有銅層及鉬層之多層薄膜用蝕刻液 - Google Patents
具有銅層及鉬層之多層薄膜用蝕刻液 Download PDFInfo
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- TWI405874B TWI405874B TW100104951A TW100104951A TWI405874B TW I405874 B TWI405874 B TW I405874B TW 100104951 A TW100104951 A TW 100104951A TW 100104951 A TW100104951 A TW 100104951A TW I405874 B TWI405874 B TW I405874B
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- Prior art keywords
- etching
- acid
- layer
- copper
- etching solution
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 167
- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 75
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 64
- 239000011733 molybdenum Substances 0.000 title claims abstract description 64
- 239000007788 liquid Substances 0.000 title claims description 35
- 239000010409 thin film Substances 0.000 title abstract 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 24
- -1 amine compound Chemical class 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 17
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 13
- 229910001431 copper ion Inorganic materials 0.000 claims description 13
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 12
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- 239000002253 acid Substances 0.000 claims description 7
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- 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
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Description
本發明係關於具有銅層及鉬層之多層薄膜用蝕刻液。尤其,本發明之蝕刻液適用於於鉬層上設置有銅層之多層薄膜之蝕刻。
以往,平面顯示器等顯示器之配線材料,一般而言使用鋁或鋁合金。然而,隨著顯示器之大型化與高解析度化,如此鋁系的配線材料中,發生導因於配線阻抗等特性的信號延遲問題,而有均勻之畫面顯示困難的傾向。
因此,阻抗較低之材料之銅或以銅為主成分的配線的利用正在研究中。然而,雖然銅具有抵抗較低的優點,但另一方面有以下缺點:作為閘極配線(gate wiring)使用時,玻璃等基板與銅之密接性不足,又,作為源極及汲極(source and drain)配線使用時,發生往作為其基底之矽半導體膜擴散的情形。因此,為防止上述問題,具有與玻璃等基板的密接性高,也兼具不易擴散至矽半導體膜之阻隔性的金屬之阻隔膜的疊層的研究正被進行中,該金屬以鉬(Mo)受到矚目。
此外,具有銅或以銅為主成分之銅合金的疊層膜,係利用濺鍍法等的成膜製程形成於玻璃等基板上,接著經由以光阻等作為光罩進行蝕刻的蝕刻步驟形成電極圖案。接著,此蝕刻步驟的方式有利用蝕刻液之濕式(wet)與利用電漿等之蝕刻氣體之乾式(Dry)。在此,濕式(wet)所使用之蝕刻液,除了追求下述幾點以外:(i)高加工精細度(ii)蝕刻殘渣少(iii)蝕刻的斑點少(iv)對於作為蝕刻對象之含銅材料之金屬的溶解,蝕刻性能安定等(槽池壽命(bathlife)的延長效果)等,為了因應顯示器的大型化及高解析度,還追求(v)將蝕刻後之剖面形狀定為特定之範圍,得到蝕刻後之良好的配線剖面形狀。更具體而言,追求:如圖1所示之銅配線端部之蝕刻面與下層之基板之間的角度(錐角(Taper angle))為30°~60°之順錐形(Taper)形狀,由光阻端部至與被設置於配線下之與阻隔膜相鄰之配線端部為止的距離為(CD差)1.2μm以下,較佳為1μm以下。
在包含銅或以銅為主成分之合金之疊層膜的蝕刻步驟,使用的蝕刻液方面,有人提出例如:含有選擇自中性鹽、無機酸與有機酸中之至少其中之一,及過氧化氫、過氧化氫安定劑的蝕刻溶液(例如專利文獻1);含有特定量:過氧化氫、有機酸、磷酸鹽、二種類之含氮添加物、氟化化合物及水的蝕刻溶液(例如專利文獻2)等。
[習知技術文獻]
[專利文獻1] 日本專利第4282927號說明書
[專利文獻2] 日本特開2004-193620號公報
本發明係有在此情況下所完成者,其目的在於提供具有銅層及鉬層之多層薄膜用蝕刻液及利用該蝕刻液之具有銅層及鉬層之多層薄膜的蝕刻方法。
本案發明人為達前述目的努力研究的結果發現,藉由在蝕刻液中配合:(A)過氧化氫;(B)不含氟原子之無機酸;(C)有機酸;(D)胺化合物;(E)吡咯環類;及(F)過氧化氫安定劑之特定組合,且將蝕刻液定為pH2.5~5的範圍可達成前述目的。
本發明係根據上述概念而完成者。即,本發明之主旨如下述。
[1]一種蝕刻液,係pH為2.5~5之具有銅層及鉬層之多層薄膜用蝕刻液,包含:
(A) 過氧化氫;
(B) 無機酸,係不含氟原子者;
(C) 有機酸;
(D) 胺化合物,係碳數為2~10,且包含胺基及羥基並且該二種基之合計基團數為二以上者;
(E) 吡咯環類;及
(F) 過氧化氫安定劑。
[2]如[1]之蝕刻液,其中,該(B)無機酸為硫酸及/或硝酸。
[3]如[1]或[2]之蝕刻液,其中,該(C)有機酸係選擇自琥珀酸、乙醇酸、乳酸、丙二酸、蘋果酸中之至少一種有機酸。
[4]如[1]至[3]中任一項之蝕刻液,其中,該(D)胺化合物係選擇自乙醇胺、1-胺基-2-丙醇、N,N-二乙基-1,3-丙二胺中之至少一種胺化合物。
[5]如[1]至[4]中任一項之蝕刻液,其中,該(E)吡咯環類為5-胺基-1H-四唑。
[6]如[1]至[5]中任一項之蝕刻液,其中,該(F)過氧化氫安定劑為苯脲。
[7]如[1]至[6]中任一項之蝕刻液,包含:(A)過氧化氫為4.5~7.5質量%;(B)無機酸為0.01~3質量%;(C)有機酸為5~13質量%;(D)胺化合物為2~7質量%;(E)吡咯環類為0.001~0.5質量%;及(F)過氧化氫安定劑為0.01~0.5質量%。
[8]如[1]至[7]中任一項之蝕刻液,其中,更預先含有銅離子200ppm。
[9]如[1]至[8]中任一項之蝕刻液,其中,該多層薄膜係於鉬層上疊層有銅層者。
[10]一種蝕刻方法,係具有銅層及鉬層之多層薄膜之蝕刻方法,其特徵為使蝕刻對象物接觸如[1]至[8]中任一項之蝕刻液。
[11]如[10]之蝕刻方法,其中,該多層薄膜係於鉬層上疊層有銅層者。
藉由本發明,可提供一種蝕刻液及利用該蝕刻液之具有銅層及鉬層之多層薄膜的蝕刻方法,該蝕刻液係在具有銅層及鉬層之多層薄膜之蝕刻步驟中,加工精細度高、蝕刻殘渣或斑點少、可延長槽池壽命(bath life)且可得到蝕刻後之良好的配線剖面形狀之可對應顯示器之大型化及高解析度化者。又,藉由該蝕刻方法,可將具有包含銅層及鉬層之多層薄膜的配線一併進行蝕刻,故可得到高生產性且可使蝕刻後之配線剖面形狀良好。
(實施發明的最佳形態)
[具有銅層及鉬層之多層薄膜用蝕刻液]
本發明之蝕刻液,係使用於具有銅層及鉬層之多層薄膜之蝕刻,其特徵為:
包含:(A)過氧化氫;(B)無機酸,係不含氟原子者;(C)有機酸;(D)胺化合物,係碳數為2~10,且包含胺基及羥基並且該二種基之合計基團數為二以上者;(E)吡咯環類;及(F)過氧化氫安定劑,且pH為2.5~5。
[(A)過氧化氫]
本發明之蝕刻液所使用之過氧化氫具有作為氧化劑而氧化銅配線的功能,且對鉬有氧化溶解的功能,該蝕刻液中的含量,較佳為3~10質量%,更佳為4.5~7.5質量%。過氧化氫的含量若為上述範圍,過氧化氫的管理較為容易且可確保適當的蝕刻速度,蝕刻量的控制較容易,故較佳。
[(B)不含氟原子之無機酸]
本發明之蝕刻液所使用之不含氟原子的無機酸,係有助於藉由(A)過氧化氫氧化之銅的溶解者,本發明中從環境保護的觀點而言,採用不含氟原子的無機酸。不含氟原子的無機酸,例如較佳為硫酸、硝酸、鹽酸、磷酸、次亞磷酸、碳酸、磺胺酸、硼酸等,此等可單獨或可混合多種使用。其中較佳為硫酸、硝酸。
蝕刻液中之(B)無機酸的含量,較佳為0.01~5質量%,更佳為0.01~3質量%。無機酸的含量,若為上述的範圍,可得到適當的蝕刻速度且可得到蝕刻後良好的配線剖面形狀。
[(C)有機酸]
本發明之蝕刻液所使用之有機酸,係有助於銅及鉬之蝕刻及鉬來源之殘渣的去除者,該蝕刻液中的含量,較佳為1~15質量%,更佳為5~13質量%。有機酸的含量若為上述範圍內,銅及鉬的蝕刻及鉬來源的殘渣的去除可被充分進行且可得到蝕刻後之良好的配線剖面形狀。又,也可發揮作為蝕刻後所含有之銅離子的遮蔽劑(masking reagent)的功能,抑制銅所造成之過氧化氫的分解。
有機酸,碳數1~18之脂肪族羧酸、碳數6~10之芳香族羧酸以外,較佳為例如碳數1~10之胺基酸等。
碳數1~18之脂肪族羧酸,較佳為例如:甲酸、乙酸、丙酸、乳酸、乙醇酸、二乙醇酸、丙酮酸、丙二酸、丁酸、羥基丁酸、酒石酸、琥珀酸、蘋果酸、順丁烯二酸、反丁烯二酸、戊酸、戊二酸、伊康酸、己二酸、己酸、己二酸、檸檬酸、丙三羧酸(Propanetricarboxylic Acid)、反烏頭酸(trans-Aconitic acid)、庚酸(enanthic acid)、辛酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、油酸、亞麻油酸(linoleic acid)、次亞麻油酸(linolenic acid)等。
碳數6~10之芳香族羧酸,較佳為例如:安息香酸、水楊酸、杏仁酸(mandelic acid)、鄰苯二甲酸、間苯二甲酸、對苯二甲酸等。
又,碳數1~10之胺基酸,例如:胺基甲酸(carbamic acid)、丙胺酸、甘胺酸、天冬醯胺、天門冬胺酸、肌胺酸、絲胺酸、麩胺醯胺(glutamine)、麩胺酸(glutamate)、4-胺基丁酸、亞胺基二丁酸、精胺酸、白胺酸、氮三乙酸(nitrilotriacetic acid)等。
有機酸,上述有機酸中,較佳為:乙酸、琥珀酸、丙胺酸、檸檬酸、蘋果酸、乳酸、乙醇酸、酒石酸、丙二酸、甘胺酸、戊二酸、順丁烯二酸、反烏頭酸;其中,琥珀酸、蘋果酸、乳酸、乙醇酸、丙二酸尤佳,此等可單獨使用也可組合多種使用。
[(D)胺化合物]
本發明之蝕刻液所使用之胺化合物,有助於蝕刻後之良好的配線剖面形狀,係碳數為2~10,且包含胺基及羥基並且該二種基之合計基團數為二以上者。
如此之胺化合物,宜為例如:乙二胺、三亞甲基二胺、四亞甲基二胺、1,2-丙二胺、1,3-丙二胺、N,N-二甲基-1,3-丙二胺、N,N-二乙基-1,3-丙二胺、1,3-二胺基丁烷、2,3-二胺基丁烷、五亞甲基二胺、2,4-二胺基戊烷、六亞甲基二胺、七亞甲基二胺、八亞甲基二胺、九亞甲基二胺、N-甲基乙二胺、N,N-二甲基乙二胺、三甲基乙二胺、N-乙基乙二胺、N,N-二乙基乙二胺、三乙基乙二胺、1,2,3-三胺基丙烷、聯胺(hydrazine)、參(2-胺基乙基)胺、肆(胺基甲基)甲烷、二亞乙基三胺(Diethylenetriamine)、三亞乙基四胺、四亞乙基五胺、七亞乙基八胺、九亞乙基十胺、二氮雜二環十一碳烯(Diazabicycloundecene)等聚胺,乙醇胺、N-甲基乙醇胺、N-甲基二乙醇胺、N-乙基乙醇胺、N-胺基乙基乙醇胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、三乙醇胺、1-胺基-2-丙醇、N-甲基異丙醇胺、N-乙基異丙醇胺、N-丙基異丙醇胺、2-胺基丙-1-醇(2-aminopropan-1-ol)、N-甲基-2-胺基丙-1-醇、N-乙基-2-胺基丙-1-醇、1-胺基丙-3-醇、N-甲基-1-胺基丙-3-醇、N-乙基-1-胺基丙-3-醇、1-胺基丁-2-醇、N-甲基-1-胺基丁-2-醇、N-乙基-1-胺基丁-2-醇、2-胺基丁-1-醇、N-甲基-2-胺基丁-1-醇、N-乙基-2-胺基丁-1-醇、3-胺基丁-1-醇、N-甲基-3-胺基丁-1-醇、N-乙基-3-胺基丁-1-醇、1-胺基丁-4-醇、N-甲基1-胺基丁-4-醇、N-乙基-1-胺基丁-4-醇、1-胺基-2-甲基丙-2-醇、2-胺基-2-甲基丙-1醇、1-胺基戊-4-醇、2-胺基-4-甲基戊-1-醇、2-胺基己-1-醇、3-胺基庚-4-醇、1-胺基辛-2-醇、5-胺基辛-4-醇、1-胺基丙-2,3-二醇、2-胺基丙-1,3-二醇、參(羥甲基)胺基丙烷、1,2-胺基丙-3-醇、1,3-二胺基丙-2-醇、2-(2-胺乙氧基)乙醇、2-(2-胺乙胺基)乙醇、二甘醇胺等烷醇胺(alkanolamine),此等可單獨或也可組合多種使用。其中,乙醇胺、1-胺基-2-丙醇、N,N-二乙基-1,3-丙二胺尤佳。
本發明之蝕刻液所使用之胺化合物的含量,較佳為1~10質量%,更佳為2~7質量%。胺化合物的含量若為上述範圍內,可得到蝕刻後之良好的配線剖面形狀。
[(E)吡咯環類]
本發明之蝕刻液所使用之吡咯環類,較佳為例如:1H-苯并三唑、5-甲基-1H-苯并三唑、3-胺基-1H-三唑等三唑(triazole)類;1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑等四唑(terazole)類;1H-咪唑、1H-苯并咪唑等咪唑(imidazole)類;1,3-噻唑、4-甲基噻唑等噻唑(thiazole)類。此等中,四唑類較佳,其中又以5-胺基-1H-四唑更佳。
蝕刻液中之吡咯環類的含量,較佳為0.001~1質量%,更佳為0.001~0.5質量%。吡咯環類的含量若為上述範圍內,抑制蝕刻後之CD差增大且可得到蝕刻後之良好的配線剖面形狀。
[(F)過氧化氫安定劑]
本發明之蝕刻液含有過氧化氫安定劑。過氧化氫安定劑,只要是作為通常之過氧化安定劑使用者即可使用,並無限制,例如苯脲、烯丙基脲、1,3-二甲基脲、硫脲等尿素系過氧化氫安定劑以外,苯乙醯胺、苯乙二醇等為宜,其中又以苯脲較佳。
本發明之蝕刻液中之(F)過氧化氫安定劑的含量,就得到其充分的添加效果的觀點來看,較佳為0.01~0.5質量%,更佳為0.01~0.3質量%。
[pH]
本發明之蝕刻液必須為pH2.5~5。若未滿pH2.5,則鉬被蝕刻溶解時所生成之鉬氧化物難以溶解,結果,產生蝕刻後鉬氧化物來源的殘渣,變成滲漏(leak)原因,電器特性下降。又,若大於pH5,則(A)過氧化氫的安定性降低,銅配線的蝕刻速度變慢,槽池壽命也減少。由如此觀點,本發明之蝕刻液的pH值宜為2.5~5。
[銅離子]
本發明之蝕刻液,從使用初期開始提升蝕刻性能之目的的情況下,宜預先含有銅離子。銅離子,可藉由在蝕刻液添加銅粉末、硫酸銅、硝酸銅等的銅鹽,使蝕刻液中含有銅離子。
蝕刻液中之銅離子的濃度,較佳為100ppm以上,更佳為200ppm以上。又,濃度的上限為只要不降低蝕刻性能則無限制,但若考慮槽池壽命等,較佳為2000ppm以下,更佳為1000ppm以下。
[其他成分]
本發明之蝕刻液,上述(A)~(F)成分以外,也可在不妨害到蝕刻液效果的範圍含有水、通常使用於其他蝕刻液之添加劑。水,利用蒸餾、離子交換處理、過濾處理、各種吸附處理等,已除去金屬離子或有機不純物、微粒粒子等者為佳,尤其純水、超純水更佳。
[具有銅層及鉬層之多層薄膜的蝕刻方法]
本發明之蝕刻方法係將具有銅層及鉬層之多層薄膜進行蝕刻的方法,包含蝕刻對象物與本發明之蝕刻液接觸的步驟,其特徵為利用本發明之蝕刻液,即包含:(A)過氧化氫;(B)不含氟原子之無機酸;(C)有機酸;(D)碳數為2~10,且包含胺基及羥基並且該二種基之合計基團數為二以上之胺化合物;(E)吡咯環類;及(F)過氧化氫安定劑;且pH為2.5~5之具有銅層及鉬層之多層薄膜用蝕刻液。又,利用本發明之蝕刻方法,可將具有包含銅層及鉬層的多層薄膜一併進行蝕刻,且可得到蝕刻後之良好的配線剖面形狀。
本發明之蝕刻方法中,蝕刻液例如圖1所示,在玻璃等基板上依序將由鉬系材料構成之阻隔膜(barrier film,鉬層),與由銅或以銅為主成分之材料所構成之銅配線(銅層)疊層而成之具有銅層及鉬層之多層薄膜上,接著塗佈光阻,曝光轉寫所要的圖案光罩,顯影,將形成所期望的光阻圖案者作為蝕刻對象物。在此,本發明中,具有銅層及鉬層之多層薄膜,包含例如如圖1在鉬層上存在有銅層的態樣,更包含在該銅層上存在有鉬層的態樣。又,如此般之具有銅層及鉬層的多層薄膜,適用於平面顯示器等顯示器等的配線。因此,鉬層上存在有銅層之蝕刻對象物,就利用領域的觀點來看,也為較佳態樣。
銅配線,只要由銅或以銅為主成分之材料構成即可並無特別限制,形成該阻隔膜之鉬係材料可舉例如鉬(Mo)金屬或Mo合金等。
使蝕刻對象物接觸蝕刻液的方法並無特別限制,例如可利用將蝕刻液以滴下(葉片式旋轉處理)或噴霧等的形式與對象物接觸的方法,或使對象物浸漬於蝕刻液的濕式(wet)蝕刻方法。本發明中宜利用將蝕刻液滴至對象物(葉片式旋轉處理)使接觸的方法、將對象物浸漬於蝕刻液使接觸的方法。
蝕刻液之使用溫度,較佳為20~60℃,尤佳為30~50℃。蝕刻液之溫度若為20℃以上,則蝕刻速度不會過慢,生產效率不會顯著下降。相反的,若為未滿沸點的溫度,則抑制液組成變化,可維持一定的蝕刻條件。利用提升蝕刻的溫度提高蝕刻速度,然而在一併考慮抑制蝕刻液之組成變化使較小的情況可適當決定最適溫度。
本發明之蝕刻方法中,蝕刻液所含之過氧化氫,如上述般被銅或鉬之氧化溶解等消耗,又,因為該等溶解之銅或鉬促進過氧化氫之分解,而有發生起因於過氧化氫濃度降低之蝕刻液性能下降的情形。在這種情況,藉由適當地同時或分別添加(A)過氧化氫及(B)遮蔽金屬的有機酸,可延長槽池壽命。
[實施例]
接著,藉由實施例更詳細說明本發明,但本發明並不限於此等實施例。
(蝕刻後之具有銅層及鉬層之多層薄膜的剖面的觀察)
將在實施例及比較例所得到之蝕刻後之具有銅層及鉬層之多層薄膜試料切斷,使用掃描式電子顯微鏡(「S5000形(型號);日立製」),以觀察倍率30000倍(加速電壓2kV,加速電流10μA)觀察。根據SEM圖像,得到以圖1表示之錐角、CD差(μm)。
錐角、CD差(μm)若在表1記載的範圍內則視為合格,以判斷蝕刻液的性能。
(蝕刻殘渣的評價)
將在實施例及比較例所得到之蝕刻後之具有銅層及鉬層之多層薄膜試料的表面,使用掃描式電子顯微鏡(「S5000形(型號)」;日立製),以觀察倍率50000倍(加速電壓2kV,加速電流10μA)觀察,將該試料之殘渣以下述基準評價。
○:完全未發現殘渣
△:發現有些許殘渣,對配線性能無影響,無實用上的問題
×:發現有明顯殘渣
[製作例](具有銅層及鉬層之多層薄膜的製作)
以玻璃作為基板,將鉬(Mo)濺渡形成由鉬構成之阻隔膜(鉬層),接著濺鍍以銅為主成分之材料,形成以銅為主成分之配線(銅層),再接著塗佈光阻,將圖案光阻曝光轉寫後,顯影,製作在形成有圖案之鉬層上疊層有銅層之具有銅層及鉬層之多層薄膜。
[實施例1~5]
關於將製作例所得到之具有銅層及鉬層之多層薄膜,以表2所示之蝕刻液,藉由噴灑噴霧,在35℃反覆進行蝕刻作業,所得到之蝕刻後之具有銅層及鉬層之多層薄膜試料:利用上述方法,利用SEM觀察得到該蝕刻液中之銅離子濃度(表示為Cu濃度)為低濃度域(200-1000ppm,表示為Cu低濃度域)及高濃度域(3000-4000ppm,表示為Cu高濃度域)之錐角、CD差。
又,利用目視,將判斷光阻未圖案成形區域之蝕刻對象物完成蝕刻之時間定為恰當蝕刻(just etching)時間,將以該恰當蝕刻時間之110~300%範圍內之任意比例蝕刻處理(過蝕刻,over-etching)的時間設定為蝕刻時間(例如恰當蝕刻時間100秒時,若為50%之過蝕刻,其蝕刻時間為150秒)此等之評價如表2所示。
*1,三菱瓦斯化學股份有限公司製
*2,和光純藥工業股份有限公司製
*3,5-胺基-1H-四唑,和光純藥工業股份有限公司製
*4,苯脲,和光純藥工業股份有限公司製
[實施例6及7]
實施例4中,除了於所欲使用之蝕刻液4預先添加銅粉末,使銅離子濃度為200ppm、6000ppm以外,以與實施例4同樣的方式進行蝕刻,分別定為實施例6及7。第一次蝕刻所得到之具有銅層及鉬層之多層薄膜的錐角、CD差、殘渣的評價如表3所示。又,於表3中表示實施例4之第一次蝕刻所得到之具有銅層及鉬層之多層薄膜之錐角、CD差及殘渣評價。
[比較例1~5]
實施例1中除了蝕刻液利用如表4所示調配者以外,以與實施例1同樣的方法進行蝕刻。將得到之具有銅層及鉬層之多層薄膜的錐角、CD差(μm)、殘渣評價表示如表4。
*5,在Cu高濃度域,配線剖面形狀中,下層之鉬較上層之銅被選擇性地蝕刻,發生底切。
*6,未被蝕刻
*7,光阻剝落
使用本發明之蝕刻液的實施例,蝕刻後之配線剖面形狀良好,且殘渣評價方面也顯示出優異的結果。然而,使用不含(B)成分之蝕刻液的比較例1,配線剖面形狀中,下層之鉬較上層之銅被選擇性地蝕刻,發生所謂底切(undercut)。使用不含(B)~(F)成分之蝕刻液的比較例2及3,未蝕刻,或光阻剝離,確認此等蝕刻液無法實際應用。又,使用pH為本發明限定範圍以外之蝕刻液的比較例4,CD差大於1,使用不含(D)成分之蝕刻液的比較例5,下層之鉬被選擇性蝕刻,蝕刻端面非呈順錐形,部分形成錐角超過90°的逆錐形,發生配線剖面形狀方面的問題。
使用預先含有銅離子200ppm或6000ppm之蝕刻液之實施例6及7之第一次蝕刻後的配線剖面形狀,相較於實施例4之第1次之蝕刻後之配線剖面形狀,較佳,殘渣評價方面也良好。即,證實於本發明之蝕刻液預先添加銅離子,則從蝕刻液之使用初期開始,可發現良好的性能。
本發明之蝕刻液,適用於具有銅層及鉬層之多層薄膜的蝕刻,使用該蝕刻液之蝕刻方法,可將具有含銅層及鉬層之多層薄膜的配線一起蝕刻,且蝕刻後之配線剖面形狀良好,可完成高生產性。
[圖1]利用本發明之蝕刻液蝕刻時之具有含銅層及鉬層之多層薄膜之配線剖面的模式圖。
Claims (9)
- 一種蝕刻液,係pH為2.5~5之具有銅層及鉬層之多層薄膜用蝕刻液,包含:(A)過氧化氫;(B)無機酸,係不含氟原子者;(C)有機酸,係選擇自琥珀酸、乙醇酸、乳酸、丙二酸、蘋果酸中之至少一種;(D)胺化合物,係碳數為2~10,且包含胺基及羥基並且該二種基之合計基團數為二以上者;(E)5-胺基-1H-四唑;及(F)過氧化氫安定劑。
- 如申請專利範圍第1項之蝕刻液,其中,該(B)無機酸為硫酸及/或硝酸。
- 如申請專利範圍第1或2項之蝕刻液,其中,該(D)胺化合物係選擇自乙醇胺、1-胺基-2-丙醇、N,N-二乙基-1,3-丙二胺中之至少一種胺化合物。
- 如申請專利範圍第1或2項之蝕刻液,其中,該(F)過氧化氫安定劑為苯脲。
- 如申請專利範圍第1或2項之蝕刻液,包含:(A)過氧化氫為4.5~7.5質量%;(B)無機酸為0.01~3質量%;(C)有機酸為5~13質量%;(D)胺化合物為2~7質量%;(E)5-胺基-1H-四唑為0.001~0.3質量%;及(F)過氧化氫安定劑為0.01~0.5質量%。
- 如申請專利範圍第1或2項之蝕刻液,其中,更預先含有銅離子100~2000ppm。
- 如申請專利範圍第1或2項之蝕刻液,其中,該多層薄膜係於鉬層上疊層有銅層者。
- 一種蝕刻方法,係具有銅層及鉬層之多層薄膜之蝕刻方法,其特徵為使蝕刻對象物接觸如申請專利範圍第1至6項中任一項之蝕刻液。
- 如申請專利範圍第8項之蝕刻方法,其中,該多層薄膜係於鉬層上疊層有銅層者。
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EP2537960A1 (en) | 2012-12-26 |
CN102762770B (zh) | 2014-07-16 |
EP2537960A4 (en) | 2013-11-13 |
US20120319033A1 (en) | 2012-12-20 |
JP5051323B2 (ja) | 2012-10-17 |
EP2537960B1 (en) | 2015-04-01 |
TW201137176A (en) | 2011-11-01 |
JPWO2011099624A1 (ja) | 2013-06-17 |
CN102762770A (zh) | 2012-10-31 |
KR101271414B1 (ko) | 2013-06-05 |
WO2011099624A1 (ja) | 2011-08-18 |
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