WO2024083020A1 - 一种选择性蚀刻氧化铝的组合物 - Google Patents

一种选择性蚀刻氧化铝的组合物 Download PDF

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WO2024083020A1
WO2024083020A1 PCT/CN2023/124136 CN2023124136W WO2024083020A1 WO 2024083020 A1 WO2024083020 A1 WO 2024083020A1 CN 2023124136 W CN2023124136 W CN 2023124136W WO 2024083020 A1 WO2024083020 A1 WO 2024083020A1
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acid
etching
composition according
etching composition
aluminum oxide
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French (fr)
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赵鹏
刘兵
彭洪修
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安集微电子科技（上海）股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
    • C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K13/00—Etching, surface-brightening or pickling compositions
    • 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
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • 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
    • C23F1/32—Alkaline compositions
    • C23F1/36—Alkaline compositions for etching aluminium or alloys thereof

Definitions

  • the invention relates to the field of chemical etching, in particular to a composition for selectively etching aluminum oxide.
  • the raw materials for conductive wiring have shifted from aluminum to copper with lower resistance, and the interlayer insulating film has shifted from silicon oxide film to low dielectric constant film (film with a relative dielectric constant of less than 3. Hereinafter, it is referred to as Low-k film).
  • Low-k film silicon oxide film to low dielectric constant film
  • the increase in the current density flowing through the wiring can easily cause electromigration of copper. Therefore, the technology of using cobalt as a wiring material with high reliability instead of copper and the technology of introducing cobalt alloy as a protective metal (cap metal) to prevent electromigration of copper have been reported.
  • the aspect ratio (ratio obtained by dividing the resist film thickness by the resist line width) of the pattern in the resist with a film thickness of 1 um becomes too large, resulting in problems such as pattern collapse.
  • the following hard mask method is sometimes used: a film containing titanium or silicon (hereinafter referred to as a hard mask) is inserted between the pattern film actually to be formed and the resist film, and the resist pattern is temporarily transferred to the hard mask by dry etching, and then the hard mask is used as an etching mask to transfer the pattern to the film actually to be formed by dry etching.
  • a fluorine-based gas is selected.
  • aluminum oxide is selected as an etching stop layer, aluminum oxide has high resistance to fluorine-based gases, so it has the advantage of functioning as an etching stop layer even in a thin film.
  • the via creation is preferably achieved by using a metal hard mask, typically a TiN hard mask, and removing the metal (e.g.
  • a thin etch stop layer is deposited on the copper and/or cobalt (i.e., the copper and/or cobalt metal surface) to protect the underlying copper and/or cobalt at the bottom of the through hole to be produced.
  • This thin etch stop layer typically comprises or consists of an aluminum compound and may have a maximum thickness of 30 nm or less, in particular 20 nm or less, more in particular 10 nm or less or even 5 nm or less.
  • metal e.g., TiN
  • etch stop layer any polymer residue still in the vias.
  • materials such as low-k materials, copper metal, and/or cobalt metal should not be etched.
  • dielectric films of aluminum oxide can generally be removed by wet etching in acidic and alkaline media (see, for example, B. Zhou et al., J. Electrochem. Soc. Vol. 143(2) 619-623 (1996) or J. Oh et al., J. Electrochem. Soc. Vol. 156(4) D217-D222 (2011)), but without the etching rate accuracy and reliability required for etching thin or ultra-thin etch stop layers comprising or consisting of aluminum compounds (such as aluminum oxide).
  • the main object of the present invention is to provide a composition for selectively etching a layer of aluminum compound in the presence of a low-k material layer and/or a layer containing copper and/or cobalt, and removing organic polymer residues, which has the characteristics that allow the following: selective etching of aluminum oxide, with a higher etching rate selectivity ratio between plasma-treated aluminum oxide and non-plasma-treated aluminum oxide, while not damaging or not significantly damaging the low-k material layer and/or the layer containing copper metal and/or cobalt metal that also exists, and effectively removing organic polymer residues.
  • the object of the present invention is to provide a composition for selectively etching aluminum oxide.
  • the etching composition includes: an organic solvent, a fluorine-containing anion etchant, a corrosion inhibitor, a chelating agent, an aluminum oxide etching enhancer and water.
  • the organic solvent is selected from one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol methyl ether, 1,3-propylene glycol monoethyl ether, methoxy-1-propanol, propylene glycol propyl ether, dipropylene glycol, dipropylene glycol methyl ether, and triethylene glycol monomethyl ether.
  • the organic solvent is dipropylene glycol methyl ether.
  • the concentration of the organic solvent is 1 wt% to 30 wt%.
  • the fluorine-containing anion etchant is selected from ammonium fluoride, ammonium difluoride, triethanolammonium fluoride, diethylene glycolammonium fluoride, methyldiethanolammonium fluoride, tetramethylammonium fluoride, triethylamine trihydrofluoride, hydrogen fluoride, fluoroboric acid, tetrafluoroethylene One or more of boric acid, ammonium tetrafluoroborate, fluoroacetic acid, ammonium fluoroacetate, trifluoroacetic acid.
  • the fluorine-containing anion etchant is ammonium fluoride.
  • the concentration of the fluorine-containing anion etchant is 0.01 wt%-5 wt%.
  • the corrosion inhibitor is selected from benzotriazole, methylbenzotriazole, 5-carboxybenzotriazole, 5-phenyltetrazolyl, 1,2,4-triazole, 5-aminotetrazolyl, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, One or more of triazole, naphthalenetriazole, 1H-tetrazolyl-5-acetic acid, 1-phenyl-2-tetrazoline-5-thione, 4-methyl-2-phenylimidazole, 2-mercaptothiazoline
  • the concentration of the corrosion inhibitor is 0.01 wt%-5 wt%.
  • the chelating inhibitor is selected from one or more of lauric acid, benzoic acid, tartaric acid, ethylenediaminetetraacetic acid, iminodiacetic acid, aspartic acid, nitrilotriacetic acid, salicylic acid, 2,3-pyridinedicarboxylic acid, L-tyrosine, cinnamic acid, histidine, 1,2-cyclohexanediaminetetraacetic acid, 2,2'-azanediyldiacetic acid, ethylenediaminetetraacetic acid, 2-(2-hydroxyphenyl)-benzoxazole, 2-(2-hydroxyphenyl)-benzothiazole, pyridine, 3-methoxypyridine, 2-picoline, lutidine, piperidine, piperazine, pyrrole, pyrimidine, pyrazine, pyridazine, quinoline, indole, and 1-methylimidazole.
  • the concentration of the chelating inhibitor is 0.01 wt%-10 wt%.
  • the aluminum oxide etching enhancer is selected from one or more of 5-(2-phenylethyl)-1H-1,2,3,4-tetrazole, 5-benzyl tetrazole, 5-trityl-1H-tetrazole, 5-benzylmercaptotetrazole, 5-[(3-bromophenyl)methyl]-2H-1,2,3,4-tetrazole, 5-phenyltetrazole, benzyl alcohol, 4-methylbenzyl alcohol, 5-methylm-xylene glycol, o-benzylhydroxylamine, 4-methylbenzyloxyamine, and 3-trifluoromethylbenzyl alcohol.
  • the aluminum oxide etching enhancer is benzyl alcohol.
  • the concentration of the aluminum oxide etching enhancer is 0.1wt%-5wt%.
  • the pH value of the etching composition is 4-7.
  • the etching composition of the present invention can selectively etch the aluminum oxide layer in the presence of a low-k material layer of tungsten or cobalt, has a higher etching rate for plasma-treated aluminum oxide, and does not damage the low-k material, tungsten and cobalt material.
  • the etching compositions of Examples 1-25 and Comparative Examples 1-6 were prepared, and the components were mixed evenly.
  • An organic solvent and water were poured into a reaction cup, and then a chelating agent, a corrosion inhibitor, and a fluorine-containing anion etchant were added, and the mixture was stirred and mixed evenly at room temperature. Water was the balance and was not shown in Table 1.
  • Etch rate of aluminum oxide The etching solution was placed in a reactor and heated to 40° C. The aluminum oxide film was then placed therein for etching for 10 min, and the etching rate was calculated by measuring the thickness change before and after etching using an ellipsometer.
  • Etch rate for low-k materials The etching solution was placed in a reactor and heated to 40° C. The low BDI film was then placed therein for etching for 10 min, and the etching rate was calculated by measuring the thickness change before and after etching using an ellipsometer.
  • Etch rate of cobalt The etching solution was placed in a reactor and heated to 40° C. The cobalt film was then placed therein and etched for 10 min. The etching rate was then calculated by converting the change in resistance before and after etching into film thickness using a four-probe measurement.
  • Etch rate of tungsten The etching solution was placed in a reactor and heated to 40° C. The tungsten film was then placed in the reactor and etched for 10 min. The etching rate was calculated by converting the resistance change before and after etching into film thickness using a four-probe measurement.
  • composition of the present invention can selectively etch aluminum oxide while not damaging or not significantly damaging low-k materials, tungsten and cobalt.
  • Comparative Example 1 and Example 25 shows that without adding a fluorine-containing anion etchant, aluminum oxide cannot be etched.
  • Comparative Examples 2 and 6 and Example 25 shows that the benzotriazole corrosion inhibitor has a good protective effect on cobalt and tungsten.
  • the comparison between Comparative Example 3 and Example 25 shows that without adding a chelating agent, tungsten will be significantly corroded.
  • the comparison between Comparative Examples 4 and 5 and Example 25 shows that the aluminum oxide etching enhancer can control the etching rate of aluminum oxide.
  • the aluminum oxide etching enhancer selected in the present invention can enable the etching solution to selectively etch aluminum oxide, has a higher etching rate for plasma-treated aluminum oxide, and has an etching rate for aluminum oxide that has not been plasma-treated that is significantly lower than the etching rate for plasma-treated aluminum oxide.
  • the positive progressive effect of the present invention is that the disclosure of the present invention provides a composition for selectively etching an aluminum oxide layer in the presence of a low-k material layer of tungsten and/or cobalt, which has the following characteristics: selectively etching aluminum oxide, having a higher etching rate selectivity ratio between plasma-treated aluminum oxide and non-plasma-treated aluminum oxide, while not damaging or not significantly damaging the low-k material layer and tungsten or cobalt metal layer that also exists, and removing organic polymer residues, and has good application prospects in microelectronics fields such as semiconductor wafer cleaning.

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Abstract

本发明提供了一种选择性蚀刻氧化铝的组合物，包括：有机溶剂，含氟阴离子蚀刻剂，腐蚀抑制剂，螯合剂，氧化铝蚀刻增强剂和水。发明中的蚀刻组合物能够reclaim使用，在低-k材料层钨或钴的层存在下选择性蚀刻氧化铝层，对等离子体处理过的氧化铝有较高的刻蚀速率，同时不损害低-k材料、钨和钴材料，并去除有机聚合物残留。

Description

一种选择性蚀刻氧化铝的组合物 技术领域
本发明涉及化学蚀刻领域，尤其涉及一种选择性蚀刻氧化铝的组合物。
背景技术
近年来，随着设计标准的微细化推进，导电用布线原材料从铝向电阻更低的铜的转移、层间绝缘膜从硅氧化膜向低介电常数膜(相对介电常数小于3的膜。以下，称为Low-k膜)的转移正在推进。但是，随着布线的微细化进行，由于流过布线的电流密度增大而容易引起铜的电迁移。因此，报道了使用钴作为代替铜的可靠性高的布线材料的技术、导入钴合金作为防止铜的电迁移的保护金属(cap metal)的技术。
另外，在0.2um以下的图案的情况下，膜厚1um的抗蚀剂中图案的深宽比(将抗蚀剂膜厚除以抗蚀剂线宽而得到的比)变得过大，而产生图案倒塌等问题。为了解决该问题，有时使用如下硬掩膜法:向实际想要形成的图案膜与抗蚀剂膜之间插入包含钛或硅的膜(以下，称为硬掩膜)，利用干蚀刻将抗蚀剂图案暂时转印至硬掩膜，之后，以该硬掩膜作为蚀刻掩模，利用干蚀刻将图案转印至实际想要形成的膜。
通过干蚀刻形成通孔的工序中，进行干蚀刻直到到达作为布线材料的钴为止的情况下，有时钴被暴露于干蚀刻的气体而变质，给电特性带来影响。因此，考虑如下工序:在钴上设置蚀刻阻挡层,通过干蚀刻形成通孔直到到达蚀刻阻挡层为止，接着用对钴的影响少的方法将通孔底的蚀刻阻挡层去除，使钴露出。
通常,通过干蚀刻形成通孔时，选择氟系的气体，但若选择氧化铝作为蚀刻阻挡层，则氧化铝对氟系的气体的耐性高，因此有即使为薄的膜、也具有作为蚀刻阻挡层而发挥功能的优点
在进一步使半导体晶片上的结构减至最小的整合方案中，如在用于在半导体晶片上制造20nm结构或低于20nm结构或用于制造10nm结构或低于10nm结构的整合方案中，通孔产生优选是通过使用以下实现：金属硬屏蔽，通常为TiN硬屏蔽，及移除位于金属(例 如TiN)硬屏蔽下方的低-k材料的后续干式蚀刻步骤(且任选地通过额外层，例如非金属硬屏蔽或结合层与金属/TiN硬屏蔽分离)。为保护待产生的通孔的底部的下层铜和/或钴，通常将薄蚀刻终止层沉积于铜和/或钴(即铜和/或钴金属表面)上。此薄蚀刻终止层通常包含铝化合物或由铝化合物组成且可具有30nm或更小，尤其是20nm或更小，更尤其是10nm或更小或甚至是5nm或更小的最大厚度。
为继续进行制造方法，必须移除以下材料：1)金属(例如TiN)硬屏蔽、2)仍在通孔中的任何聚合残余物；及3)蚀刻终止层。同时，不应蚀刻诸如低-k材料、铜金属和/或钴金属的材料。
已知氧化铝的介电质膜一般可通过在酸性及碱性介质中湿式蚀刻而移除(参见例如B.Zhou等人,J.Electrochem.Soc.第143(2)卷619-623(1996)或J.Oh等人J.Electrochem.Soc.第156(4)卷D217-D222(2011))，然而不具有蚀刻包含铝化合物(例如氧化铝)或由铝化合物(例如氧化铝)组成的薄或超薄蚀刻终止层所要的蚀刻速率精确性及可靠性。
本发明的主要目的为提供一种用于在低-k材料层和/或包含铜和/或钴的层存在下选择性蚀刻铝化合物的层的组合物，并去除有机聚合物残留，其具有允许以下者的特性：选择性刻蚀氧化铝，对等离子体处理过的氧化铝和未经等离子体处理过的氧化铝有较高的刻蚀速率选择比，同时不损害或不明显损害也存在的低-k材料层和/或包含铜金属和/或钴金属的层，并有效去除有机聚合物残留。
发明内容
为了克服上述技术缺陷，本发明的目的在于提供一种选择性蚀刻氧化铝的组合物。
具体的，所述蚀刻组合物，包括：有机溶剂，含氟阴离子蚀刻剂，腐蚀抑制剂，螯合剂，氧化铝蚀刻增强剂和水。
优选的，所述有机溶剂选自乙二醇单甲醚、乙二醇单乙醚、二乙二醇单丁醚、二丙二醇单乙醚、二丙二醇甲醚、1，3-丙二醇单乙醚、甲氧基-1-丙醇、丙二醇丙醚、一缩二丙二醇、二丙二醇甲醚、三甘醇单甲醚中的一种或多种。
优选的，所述有机溶剂为二丙二醇甲醚。
优选的，所述有机溶剂的浓度为1wt％～30wt％。
优选的，所述含氟阴离子蚀刻剂选自氟化铵、二氟化铵、氟化三乙醇铵、氟化二乙二醇铵、氟化甲基二乙醇铵、氟化四甲基铵、三氢氟化三乙胺、氟化氢、氟硼酸、四氟 硼酸、四氟硼酸铵、氟乙酸、氟乙酸铵、三氟乙酸中的一种或多种。
优选的，所述含氟阴离子蚀刻剂为氟化铵。
优选的，所述含氟阴离子蚀刻剂的浓度为0.01wt％-5wt％。
优选的，所述腐蚀抑制剂选自苯并三氮唑、甲基苯并三氮唑、5-羧基苯并三唑、5-苯基四氮唑、1,2,4-三唑、5-氨基四唑、3-氨基-1H-1,2,4-三唑、3,5-二氨基-1,2,4-三唑、甲苯基三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、萘三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、4-甲基-2-苯基咪唑、2-巯基噻唑啉、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、咪唑、临苄基羟胺、羟胺、苯并咪唑、甲基四唑、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、苯并噻唑、吲唑、腺嘌呤、鸟嘌呤、胸腺嘧啶、乙二酸、丙二酸、丁二酸、吩噻嗪、1-甲基吡唑、2-羟基异丁酸甲酯、6-巯基嘌呤中的一种或多种。
优选的，所述腐蚀抑制剂的浓度为0.01wt％-5wt％。
优选的，所述螯合抑制剂选自月桂酸、苯甲酸、酒石酸、乙二胺四乙酸、亚氨基二乙酸、天冬氨酸、氨三乙酸、水杨酸、2,3-吡啶二羧酸、L-酪氨酸、肉桂酸、组氨酸、1,2-环己二胺四乙酸、2,2’-氮烷二基二乙酸、乙二胺四乙酸、2-(2-羟苯基)-苯并唑、2-(2-羟苯基)-苯并噻唑、吡啶、3-甲氧基吡啶、2-甲吡啶、二甲基吡啶、哌啶、哌嗪、吡咯、嘧啶、吡嗪、哒嗪、喹啉、吲哚、1-甲基咪唑中的一种或多种。
优选的，所述螯合抑制剂的浓度为0.01wt％-10wt％。
优选的，所述氧化铝蚀刻增强剂选自5-(2-苯基乙基)-1H-1,2,3,4-四唑、5-苄基四氮唑、5-三苯甲基-1H-四氮唑、5-苄巯基四氮唑、5-[(3-溴苯基)甲基]-2H-1,2,3,4-四唑、5-苯基四氮唑、苄醇、4-甲基苄醇、5-甲基间苯二甲醇、邻苄基羟胺、4-甲基苄氧胺、3-三氟甲基苯甲醇中的一种或多种。
优选的，所述氧化铝蚀刻增强剂为苄醇。
优选的，所述氧化铝蚀刻增强剂的浓度为0.1wt％-5wt％。
优选的，所述蚀刻组合物的pH值为4～7。
采用了上述技术方案后，与现有技术相比，具有以下有益效果：
本发明中的蚀刻组合物能够在低-k材料层钨或钴的层存在下选择性蚀刻氧化铝层，对等离子体处理过的氧化铝有较高的刻蚀速率，同时不损害低-k材料、钨和钴材料。
具体实施方式
以下结合具体实施例进一步阐述本发明的优点。
依照表1示出的各个组分及其含量，配置实施例1-25及对比例1-6的蚀刻组合物，将各个组分混匀即可，在反应杯中倒入有机溶剂，水，然后添加螯合剂，腐蚀抑制剂，含氟阴离子蚀刻剂，室温下充分搅拌混合均匀。水为余量，表1中并未示出。
表1实施例1-25及对比例1-6的组分及其含量



选取部分实施例与对比例1-6进行性能测试，其测试结果见表2。
对氧化铝的蚀刻速率将蚀刻组合液置于反应器中加热至40℃。然后将氧化铝膜放置在其中蚀刻10min，然后通过椭偏仪测量蚀刻前后厚度变化来计算蚀刻速率。
对低-k材料的蚀刻速率将蚀刻组合液置于反应器中加热至40℃。然后将低BDⅠ膜放置在其中蚀刻10min，然后通过椭偏仪测量蚀刻前后厚度变化来计算蚀刻速率。
对钴的蚀刻速率将蚀刻组合液置于反应器中加热至40℃。然后将钴膜放置在其中蚀刻10min，然后通过四探针测量蚀刻前后电阻值变化换算成膜厚来计算蚀刻速率。
对钨的蚀刻速率将蚀刻组合液置于反应器中加热至40℃。然后将钨膜放置在其中蚀刻10min，然后通过四探针测量蚀刻前后电阻值变化换算成膜厚来计算蚀刻速率。
表2实施例4、8、13、18和25与对比例1-6的测试结果
基于上述测试结果可知，本发明的组合物可以选择性地蚀刻氧化铝，同时不损害或不明显损害低-k材料、钨和钴。
具体而言，对比例1与实施列25对照表明：不添加含氟阴离子蚀刻剂，则无法对氧化铝进行刻蚀。对比例2和6与实施例25对照表明，苯并三氮唑腐蚀抑制剂，会对钴和钨有很好的保护效果。对比例3与实施例25对照表明，不添加螯合剂，会对钨有明显腐蚀。对比例4和5与实施例25对照表明，氧化铝蚀刻增强剂可以控制氧化铝的刻蚀速率。本发明中所选用的氧化铝刻蚀增强剂可以使本刻蚀液选择性刻蚀氧化铝，对等离子体处理过的氧化铝有较高的刻蚀速率，对未经等离子体处理的氧化铝的刻蚀速率明显小于等离子体处理过的氧化铝的刻蚀速率。
综上，本发明的积极进步效果在于：本发明的公开提供了一种用于在低-k材料层钨/或钴的层存在下选择性蚀刻氧化铝层的组合物，其具有允许以下者的特性：选择性刻蚀氧化铝，对等离子体处理过的氧化铝和未经等离子体处理过的氧化铝有较高的刻蚀速率选择比，同时不损害或不明显损害也存在的低-k材料层和钨或钴金属的层，并去除有机聚合物残留，在半导体晶圆清洗等微电子领域具有良好的应用前景。
应当注意的是，本发明的实施例有较佳的实施性，且并非对本发明作任何形式的限制，任何熟悉该领域的技术人员可能利用上述揭示的技术内容变更或修饰为等同的有效实施例，但凡未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何修改或等同变化及修饰，均仍属于本发明技术方案的范围内。

Claims (15)

  1. 一种选择性刻蚀氧化铝的蚀刻组合物，其特征在于，包括：
    有机溶剂，含氟阴离子蚀刻剂，腐蚀抑制剂，螯合剂，氧化铝蚀刻增强剂和水。
  2. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述有机溶剂选自乙二醇单甲醚、乙二醇单乙醚、二乙二醇单丁醚、二丙二醇单乙醚、二丙二醇甲醚、1，3-丙二醇单乙醚、甲氧基-1-丙醇、丙二醇丙醚、一缩二丙二醇、二丙二醇甲醚、三甘醇单甲醚、二甲基亚砜，环丁砜中的一种或多种。
  3. 如权利要求2所述的蚀刻组合物，其特征在于，
    所述有机溶剂为二丙二醇甲醚。
  4. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述有机溶剂的浓度为1wt％～30wt％。
  5. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述含氟阴离子蚀刻剂选自氟化铵、二氟化铵、氟化三乙醇铵、氟化二乙二醇铵、氟化甲基二乙醇铵、氟化四甲基铵、三氢氟化三乙胺、氟化氢、氟硼酸、四氟硼酸、四氟硼酸铵、氟乙酸、氟乙酸铵、三氟乙酸中的一种或多种。
  6. 如权利要求5所述的蚀刻组合物，其特征在于，
    所述含氟阴离子蚀刻剂为氟化铵。
  7. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述含氟阴离子蚀刻剂的浓度为0.01wt％-5wt％。
  8. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述腐蚀抑制剂选自苯并三氮唑、甲基苯并三氮唑、5-羧基苯并三唑、5-苯基四氮唑、1,2,4-三唑、5-氨基四唑、3-氨基-1H-1,2,4-三唑、3,5-二氨基-1,2,4-三唑、甲苯基三唑、3-氨基-5-巯基-1,2,4-三唑、1-氨基-1,2,4-三唑、1-氨基-1,2,3-三唑、1-氨基-5-甲基-1,2,3-三唑、3-巯基-1,2,4-三唑、3-异丙基-1,2,4-三唑、萘三唑、1H-四唑-5-乙酸、1-苯基-2-四唑啉-5-硫酮、4-甲基-2-苯基咪唑、2-巯基噻唑啉、2,4-二氨基-6-甲基-1,3,5-三嗪、噻唑、咪唑、临苄基羟胺、羟胺、苯并咪唑、甲基四唑、1,5-五亚甲基四唑、1-苯基-5-巯基四唑、苯并噻唑、吲唑、腺嘌呤、鸟嘌呤、胸腺嘧啶、乙二酸、丙二酸、丁二酸、吩噻嗪、1-甲基吡唑、2-羟基异丁酸甲酯、6-巯基嘌呤中的一种或多种。
  9. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述腐蚀抑制剂的浓度为0.01wt％-5wt％。
  10. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述螯合抑制剂选自月桂酸、苯甲酸、酒石酸、乙二胺四乙酸、亚氨基二乙酸、天冬氨酸、氨三乙酸、水杨酸、2,3-吡啶二羧酸、L-酪氨酸、肉桂酸、组氨酸、1,2-环己二胺四乙酸、2,2’-氮烷二基二乙酸、乙二胺四乙酸、2-(2-羟苯基)-苯并唑、2-(2-羟苯基)-苯并噻唑、吡啶、3-甲氧基吡啶、2-甲吡啶、二甲基吡啶、哌啶、哌嗪、吡咯、嘧啶、吡嗪、哒嗪、喹啉、吲哚、1-甲基咪唑中的一种或多种。
  11. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述螯合抑制剂的浓度为0.01wt％-10wt％。
  12. 如权利要求1所述的蚀刻组合物，其特征在于，
    选自5-(2-苯基乙基)-1H-1,2,3,4-四唑、5-苄基四氮唑、5-三苯甲基-1H-四氮唑、5-苄巯基四氮唑、5-[(3-溴苯基)甲基]-2H-1,2,3,4-四唑、5-苯基四氮唑、苄醇、4-甲基苄醇、5-甲基间苯二甲醇、邻苄基羟胺、4-甲基苄氧胺、3-三氟甲基苯甲醇中的一种或多种。
  13. 如权利要求12所述的蚀刻组合物，其特征在于，
    所述氧化铝蚀刻增强剂为苄醇。
  14. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述氧化铝蚀刻增强剂的浓度为0.1wt％-5wt％。
  15. 如权利要求1所述的蚀刻组合物，其特征在于，
    所述蚀刻组合物的pH值为4～7。
PCT/CN2023/124136 2022-10-18 2023-10-12 一种选择性蚀刻氧化铝的组合物 WO2024083020A1 (zh)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111465716A (zh) * 2017-12-08 2020-07-28 巴斯夫欧洲公司 用于在低-k材料、铜和/或钴的层的存在下选择性蚀刻包含铝化合物的层的组合物及方法
CN112080279A (zh) * 2019-06-12 2020-12-15 关东鑫林科技股份有限公司 蚀刻组合物
CN113736466A (zh) * 2020-05-29 2021-12-03 新应材股份有限公司 蚀刻剂组合物、增粘剂、碱溶液、移除聚酰亚胺的方法以及蚀刻工艺

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111465716A (zh) * 2017-12-08 2020-07-28 巴斯夫欧洲公司 用于在低-k材料、铜和/或钴的层的存在下选择性蚀刻包含铝化合物的层的组合物及方法
CN112080279A (zh) * 2019-06-12 2020-12-15 关东鑫林科技股份有限公司 蚀刻组合物
CN113736466A (zh) * 2020-05-29 2021-12-03 新应材股份有限公司 蚀刻剂组合物、增粘剂、碱溶液、移除聚酰亚胺的方法以及蚀刻工艺

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