CN105936822A - 用于氮化钛层的蚀刻剂组合物及使用其形成金属线的方法 - Google Patents
用于氮化钛层的蚀刻剂组合物及使用其形成金属线的方法 Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims 14
- 238000005530 etching Methods 0.000 claims abstract description 50
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 16
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 alkyl sulfonic acid Chemical compound 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 31
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 22
- 239000010937 tungsten Substances 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 claims description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-N ethanesulfonic acid Chemical compound CCS(O)(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-N 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 claims description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 abstract description 61
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 229910004205 SiNX Inorganic materials 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 3
- 229910003134 ZrOx Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000005368 silicate glass Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N peroxyacetic acid Substances CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
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Abstract
本发明提供用于TiN层的蚀刻剂组合物和使用所述蚀刻剂组合物形成金属线的方法,所述蚀刻剂组合物包括(A)以重量计75%‑95%的选自硫酸和烷基磺酸中的至少一种化合物、(B)以重量计0.3%‑10%的过氧化物、(C)以重量计0.0001%‑3%的无机铵盐以及(D)余量的水。
Description
技术领域
本申请要求2015年3月5日递交韩国知识产权局的韩国专利申请No.10-2015-0030893的优先权和权益,该韩国专利申请的全部内容通过引用并入本文。
本发明涉及用于氮化钛(TiN)层和使用其形成金属线的方法。
背景技术
使用常规光刻法图案化的光致抗蚀剂(PR)掩模具有高厚度和高蚀刻速率。此外,由于蚀刻残渣,PR掩模的使用在MTJ堆叠件上引起再沉积。
当PR掩模用于形成具有低蚀刻速率的待蚀刻的金属层的图案时,PR掩模的高蚀刻速率降低具有低蚀刻速率的待蚀刻的金属层的蚀刻选择性,并因此,引起低蚀刻斜坡。因此,这种PR掩模特征有时变成降低设备性能和防止高集成的因素。
为了解决PR掩模的这种问题,目前已使用硬掩模技术。TiN薄膜等正被用作硬掩模材料。
使用采用高密度等离子体的电感耦合等离子体反应离子刻蚀(ICPRIE)装置等进行用于TiN硬掩模的蚀刻。
作为用于TiN硬掩模的湿蚀刻方法,韩国专利No.1282177公开了用于钛基金属、钨基金属、钛钨基金属或其氮化物的包括过氧化氢、有机酸盐、氨和水的蚀刻剂。然而,除了上述方法,用于TiN硬掩模的湿蚀刻方法并非众所周知。特别是,用于对包括钨的金属层或金属线具有高选择性的TiN硬掩模的湿蚀刻方法还未被报道过。
因此,需要用于TiN硬掩模的湿蚀刻方法和用于对包括钨的金属层或金属线具有高选择性的TiN硬掩模的湿蚀刻方法。
【先行技术文献】
【专利文献】
韩国专利No.1282177
发明内容
鉴于上述情形做出本发明,以及本发明的目的是提供能够有效湿蚀刻TiN层的用于TiN层的蚀刻剂组合物。
本发明的另一目的是提供用于对包括钨的金属层或金属线具有高选择性的TiN层的蚀刻剂组合物。
本发明的另一目的是提供用于TiN层的蚀刻剂组合物,其能够选择性地蚀刻TiN层而不对低k材料(诸如TEOS和有机硅酸盐玻璃(OSG))和高k材料(诸如SiNx、SiOx、多晶Si(poly Si)、HfOx和ZrOx)和形成半导体的主要层产生损害。
本发明的另一目的是提供用于使用诸如上述的用于TiN层的蚀刻剂组合物形成金属线的方法。
本发明的一方面提供用于TiN层的蚀刻剂组合物,其包括(A)以重量计75%-95%的选自硫酸和烷基磺酸中的至少一种化合物、(B)以重量计0.3%-10%的过氧化物、(C)以重量计0.0001%-3%的无机铵盐以及(D)余量的水。
本发明的另一方面提供用于形成金属线的方法,当包括钨(W)的金属层或金属线存在于下面时,其使用TiN层作为在其上的硬掩模,所述方法包括相对于包括钨(W)的金属层或金属线选择性地蚀刻TiN层硬掩模,其中使用本发明的蚀刻剂进行蚀刻。
具体实施方式
本发明涉及用于TiN层的蚀刻剂组合物,其包括(A)以重量计75%-95%的选自硫酸和烷基磺酸中的至少一种化合物、(B)以重量计0.3%-10%的过氧化物、(C)以重量计0.0001%-3%的无机铵盐以及(D)余量的水。
TiN层意指用TiN形成的层,不考虑其用途。例如,TiN层可以形成金属线或可以用作TiN硬掩模。
在包括钨(W)的金属层或金属线的存在的情况下,用于TiN层的蚀刻剂组合物可能对选择性地蚀刻TiN层有用。
在本发明的用于TiN层的蚀刻剂组合物中,TiN层相对于与包括钨的金属层或金属线的选择性蚀刻比是8:1或更大。
在本发明的用于TiN层的蚀刻剂组合物中,选自硫酸和烷基磺酸中的至少一种化合物(A)与过氧化物组分(B)的重量比优选为100:0.32至100:7.0并且更优选为100:2至100:4。当该重量比在上述范围之外时,TiN/W蚀刻选择性可能不是8或更高,或用于TiN层的蚀刻速率变得太低引起加工时间的增加,其不利地影响加工生产量。
在本发明的用于TiN层的蚀刻剂组合物中,选自硫酸和烷基磺酸中的至少一种化合物(A)发挥控制TiN层与W层的蚀刻量和蚀刻选择性的功能。
烷基磺酸可以从甲基磺酸、乙基磺酸、丙基磺酸和丁基磺酸中选择,并且这些可以以一种类型单独使用,也可以两种类型或更多种类型结合使用。
在成分(A)中可能更优选使用硫酸。
所述选自硫酸和烷基磺酸中的至少一种化合物(A)相对于组合物的总重量以重量计的75%-95%并且更优选以重量计的80%-90%被包括。当所述组分以小于以重量计的75%被包括时,过氧化物和水的含量相对增加并且对W的蚀刻速率增加,引起减小TiN/W的蚀刻选择性的问题,而且当所述组分以大于以重量计的95%被包括时,对TiN的蚀刻速率变得太小,引起加工产率的问题,其不优选。
本发明的过氧化物(B)发挥增加对TiN的蚀刻速率并通过氧化钨层控制对工艺中所需的钨层蚀刻速率的作用。
过氧化物可以从过氧化氢(H2O2)、叔丁基氢过氧化物、过氧化月桂酰、过乙酸叔丁酯(tert-butyl peracetate)、过氧化苯甲酸叔丁酯,过氧化甲乙酮、过氧化苯甲酰和过氧化二异丙苯等中选择,并且这些可以以一种类型单独使用,也可以两种类型或更多种类型结合使用。
在这些过氧化物中,可能更优选使用过氧化氢。
所述过氧化物(B)以相对于组合物的总重量的以重量计的0.3%-10%并且更优选以重量计的1%-5%被包括。当所述组分以小于以重量计的0.3%被包括时,对TiN的蚀刻速率变得太小,其引起加工产率的问题,而当所述组分以大于以重量计的10%被包括时,对TiN层的选择性蚀刻变得困难,其不优选。
本发明中的无机铵盐(C)发挥防止由过氧化氢或过氧化物引起的钨氧化并减小对钨的蚀刻速率的作用。因此,无机铵盐(C)发挥增加对TiN/W的蚀刻选择性的作用。
无机铵盐(C)可以从例如磷酸铵、硫酸铵、硝酸铵、硼酸铵、过硫酸铵等中选择,并且这些可以以一种类型单独使用,也可以以两种类型或更多种类型结合使用。特别地,与其他无机铵盐相比,更优选硫酸铵,因为其发挥防止钨氧化的作用从而增加TiN/W选择性同时减小对W的蚀刻速率以起保护作用,并因此在增加加工利润方面具有显著效果。
作为无机铵盐(C),氟化铵可能通过蚀刻诸如SiOx,多晶Si,HfOx和ZrOx之类的高k材料,或蚀刻诸如TEOS和OSG之类的低k材料引起降低设备电气性能的问题,因此,可以排除该使用。
所述无机铵盐(C)可以以重量计的0.0001%-3%并且更优选以重量计的0.001%-1%被包括。当所述无机铵盐以小于以重量计的0.0001%被包括时,对钨的蚀刻速率可能被减小,而当所述无机铵盐以大于以重量计的3%被包括时,铵盐在的单工具处理过程中发生重结晶引起颗粒缺陷。
在本发明的用于TiN层的蚀刻剂组合物中的水(D)无特别限制,然而,优选使用去离子水,而且更优选具有比电阻值(表示水中离子去除程度的值)为18MΩ/cm或更大的去离子水。
除了上述组分以外,本发明的用于TiN层的蚀刻剂组合物还可以包括,常用添加剂,并且该添加剂可以包括阻蚀剂、金属离子螯合剂,表面活性剂等。此外,该添加剂不限于此,并且可以选择和使用本领域已知的各种其他添加剂以提高本发明的效果。
用在本发明中的选自硫酸和烷基磺酸中的至少一种化合物(A)、过氧化物(B)、无机铵盐(C)和添加剂等可以使用本领域通常已知的方法制备,并且本发明用于蚀刻的组合物优选具有用于半导体工艺的纯度。
此外,本发明提供用于形成金属线的方法,当包括钨的金属层或金属线存在于下面时,其使用TiN层作为在其上的硬掩模,所述包括相对于含钨的金属层或金属线选择性地蚀刻TiN层硬掩模,其中使用本发明的蚀刻剂进行蚀刻。
上述对用于TiN层的蚀刻剂组合物所做的描述也可以应用于用于形成金属线的方法中。
在用于形成金属线的方法中,上TiN掩模相对于包括钨的下金属层或金属线的选择性蚀刻比是8:1或更高。
在下文中,将参考实施例对本发明更详细地描述。然而,以下实施例用于更具体地描述本发明,而本发明的范围不限于以下实施例。以下实施例可以由本领域技术人员在本发明范围内适当修改或改变。
<实施例1-12和比较例1-6>用于TiN层的蚀刻剂组合物的制备
实施例1-12和比较例1-6中的用于TiN层的蚀刻剂组合物以列于下表1和下表2中的组合物和含量制备。在以下实施例和比较例中,96%的硫酸和31%的过氧化氢用作硫酸和过氧化氢,并且以纯硫酸和纯过氧化氢含量(净含量)计算其含量,并将其列于表1中。
表1
(单位:%重量)
【注】
AS:硫酸铵
APS:过硫酸铵
APM:磷酸铵
AN:硝酸铵
MSA:甲基磺酸
TBHP:叔丁基氢过氧化物
MEKP:过氧化甲乙酮
TMAH:四甲基氢氧化铵
测试例:对蚀刻性能的评价
形成有TiN层、W层、SiNx层、SiOx层、多晶Si层和HfOx层的基板在75℃下在实施例1-12和比较例1-6的蚀刻剂组合物中浸渍5min。通过使用椭圆率测量仪(SE-MG-1000)测量层厚度的变化测定基板各层的蚀刻速率,且结果如下表2所示。下表中数值单位是
表2
(单位:)
基于表2确定,在实施例1-12的用于TiN层的蚀刻剂组合物中得到的对TiN层和W层的蚀刻速率比一定水平高,对TiN/W的蚀刻选择性是8或更高,并且用组合物处理前与处理后,诸如SiNx,SiOx,多晶Si,HfOx和TEOS的低k层、半导体的主要层的厚度不变。特别是,实施例1和实施例5具有10或更高的TiN/W蚀刻选择性并在实施例中表现出显著效果。
同时,在比较例1、比较例2和比较例4-6中,未得到目标TiN/W选择性,并且特别是在比较例1和比较例2中在多晶Si层鉴定有缺陷。在比较例3中,得到了目标蚀刻性能,然而,当使用单工具时发生AS沉淀的问题。在比较例5中,对TiN的蚀刻速率太低。
本发明用于TiN层的蚀刻剂组合物能使对TiN层有效湿蚀刻。
此外,本发明用于TiN层的蚀刻剂组合物具有对包括钨的金属层或金属线的高选择性,并因此,甚至在形成包括钨的金属层或金属线时也能够选择性蚀刻。
更进一步地,本发明用于TiN层的蚀刻剂组合物能够选择性蚀刻TiN层而不对低k材料(诸如TEOS和有机硅酸盐玻璃(OSG)之类)和高k材料(诸如SiNx、SiOx、多晶Si、HfOx和ZrOx之类),形成半导体的主要层产生损害。
此外,特别地,本发明用于TiN层的蚀刻剂组合物在蚀刻TiN硬掩模中非常有用。
Claims (10)
1.用于TiN层的蚀刻剂组合物,包括:
(A)以重量计75%-95%的选自硫酸和烷基磺酸中的至少一种化合物;
(B)以重量计0.3%-10%的过氧化物;
(C)以重量计0.0001%-3%的无机铵盐;以及
(D)余量的水。
2.根据权利要求1所述的用于TiN层的蚀刻剂组合物,用于在包括钨的金属层或金属线存在的情况下有选择地蚀刻TiN层。
3.根据权利要求1所述的用于TiN层的蚀刻剂组合物,其中所述TiN层相对于包括钨的金属层或金属线的选择性蚀刻比是8:1或更高。
4.根据权利要求1所述的用于TiN层的蚀刻剂组合物,其中(A)组分与(B)组分的重量比为100:0.32至100:7.0。
5.根据权利要求1所述的用于TiN层的蚀刻剂组合物,其中所述烷基磺酸是选自由甲基磺酸、乙基磺酸、丙基磺酸和丁基磺酸组成的组中的至少一种。
6.根据权利要求1所述的用于TiN层的蚀刻剂组合物,其中所述过氧化物是选自由过氧化氢、叔丁基氢过氧化物、过氧化月桂酰、过乙酸叔丁酯、过氧化苯甲酸叔丁酯,过氧化甲乙酮、过氧化苯甲酰和过氧化二异丙苯组成的组中的至少一种。
7.根据权利要求1所述的用于TiN层的蚀刻剂组合物,其中所述无机铵盐是选自由磷酸铵、硫酸铵、硝酸铵、硼酸铵、过硫酸铵组成的组中的至少一种。
8.根据权利要求7所述的用于TiN层的蚀刻剂组合物,其中所述无机铵盐是硫酸铵。
9.用于形成金属线的方法,当包括钨的金属层或金属线存在于下部且,其使用TiN层作为在其上的硬掩模,所述方法包括:
相对于包括钨的金属层或金属线选择性地蚀刻TiN层硬掩模,其中使用根据权利要求1所述的蚀刻剂组合物进行蚀刻。
10.根据权利要求9所述的用于形成金属线的方法,其中,上TiN硬掩模相对于包括钨的下金属层或金属线的选择性蚀刻比是8:1或更高。
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CN116057151A (zh) * | 2020-08-04 | 2023-05-02 | 荣昌化学制品株式会社 | 用于调节氮化钛膜对钨膜的蚀刻选择比的蚀刻液组合物及利用其的蚀刻方法 |
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JP7175310B2 (ja) * | 2018-06-07 | 2022-11-18 | 東京エレクトロン株式会社 | 基板処理装置および基板処理方法 |
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