CN102304327A - 一种基于金属Co的抛光工艺的抛光液 - Google Patents
一种基于金属Co的抛光工艺的抛光液 Download PDFInfo
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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
- 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
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- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
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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
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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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
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/32115—Planarisation
- H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
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Abstract
本发明属于微电子工艺中技术领域,具体为一种基于金属Co的抛光工艺的抛光液。该抛光液包含0-5%比重的氧化剂,0.1-25%的比重的研磨颗粒,0.001-10%比重的螯合剂,0.01-10%比重的抑制剂,以及余量的水。所述抑制剂为2巯基噻唑啉,2巯基苯骈噻唑,或其它噻唑衍生物,或他们之中几种的混合物。所述抛光液pH值范围为3-5。本发明的抛光液所使用抑制剂能同时有效抑制铜和钴的静态腐蚀,降低铜和钴的抛光速率,因而有效降低抛光过后缺陷的产生。
Description
技术领域
本发明属于微电子工艺中技术领域,具体涉及一种用于微电子抛光工艺的抛光液。
背景技术
随着超大规模集成电路(ULSI)技术向更小器件尺寸发展,后端铜互连的尺寸也随之缩小。为减小互连延时,铜互连结构中的阻挡层和粘附层越来越薄,传统的铜粘附层/阻挡层-Ta/TaN已经不能满足要求,因为Ta相对的高电阻率,以及Ta不能作为铜直接电镀的籽晶层。金属钴(Co)价格相对便宜,和铜有很好的粘附性,Cu在Co上容易成核,同时Co的电阻率较低,同时也能作为铜的直接电镀籽晶层。钴或者钴的合金作为铜互连结构中铜的粘附层已经有一些实验报道。
在目前的化学机械抛光过程中,为减小低K介质在化学机械抛光过程中的损伤,目前使用的大多数铜和阻挡层的抛光液是酸性的。但实验发现,在含有氧化剂(H2O2)的酸性溶液中,铜和钴都极易溶解,这使得在抛光过程中,铜钴的抛光速率过快,容易导致铜的蝶形坑(dishing)出现。而钴的溶解很容易造成沟槽中钴的溶解进而导致铜的脱附。所以在酸性抛光液中加入抑制剂十分必要。加入合适的抑制剂后,可以避免酸性抛光液中铜钴抛光速度过快,引起选择性问题;同时能有效抑制铜互连结构中沟槽侧壁处钴的溶解,有效提高钴作为铜粘附层的可靠性。
发明内容
本发明的目的在于提供一种可以避免酸性抛光液中铜钴抛光速度过快,而引起选择性问题的用于微电子抛光工艺的抛光液。
本发明涉及以钴作为集成电路的一个金属层,进行抛光的抛光工艺。在集成电路中,Co主要作为铜互连的阻挡层和黏附层,但是Co也可以作为纳米晶在存储器中使用,作为金属栅在MOSFET中使用。凡是利用Co或者Co的合金、Co的化合物在电路中使用,并需要进行抛光工艺的,都属于本发明所述抛光工艺范围之内。
本发明提供的用于微电子抛光工艺的抛光液。其组分包括:0-5 %的氧化剂,0.1-25 %的研磨颗粒,0.001-10 %的螯合剂,0.01-10 % 抑制剂,以及余量的水。其中,百分比均为重量百分比,所述抑制剂为2巯基噻唑啉、2巯基苯骈噻唑或其它噻唑衍生物,或者为他们之中几种的混合物。所述抛光液PH值范围为3-5。本发明的抛光液所使用抑制剂能同时有效抑制铜和钴的静态腐蚀,降低铜和钴的抛光速率,因而有效降低抛光过后缺陷的产生。
本发明提供的CMP抛光液中有一种氧化剂。氧化剂的作用是将金属铜,钴已经阻挡层金属氧化为相应的金属氧化物,氢氧化物或者离子。所述抛光液中氧化剂可选自于过氧化氢,过硫酸铵,高碘酸钾,高氯酸钾中的一种或者其中几种的混合物;其中优选过氧化氢作为氧化剂。氧化剂所占重量比例可为0-5%;其中优选氧化剂重量比例为0.5%-5% ,更优选0.5%-3%。
本发明提供的CMP抛光液至少含有一种研磨颗粒。研磨颗粒作用是通过机械摩擦去除与研磨颗粒接触的金属或者金属的反应物,达到机械去除的目的。研磨颗粒可选自于常用的二氧化硅,二氧化铈,或三氧化二铝纳米颗粒。其中优选二氧化硅溶胶作为研磨颗粒。研磨颗粒的粒子直径可为10-100nm。研磨颗粒重量比例根据所需抛光速率可为0.1-25%。其中优选研磨颗粒重量比例为1-5%。
本发明提供的CMP抛光液至少含有一种螯合剂。螯合剂的作用是与抛光表面以及抛光液中的金属离子形成螯合物,有助于减小抛光液中的金属颗粒和抛光金属表面的金属离子污染。所用螯合剂可选自于氨基酸中的一种或者几种,如甘氨酸,谷氨酸,亮氨酸,精氨酸;以及其他有机酸,如柠檬酸。其中优选甘氨酸作为螯合剂。螯合剂的比重可为0.001-10%。其中优选螯合剂比重为0.4%。
本发明提供的CMP抛光液至少含有一种抑制剂。抑制剂的作用是降低铜和钴在抛光液中的静态腐蚀速率,有助于增大抛光平坦化速率以及减低蝶形坑缺陷和防止沟槽侧壁粘附层的溶解。所用抑制剂为2巯基噻唑啉,2巯基苯骈噻唑,其它噻唑衍生物,或他们之中几种的混合物。其中优选2巯基噻唑啉作为抑制剂。2巯基噻唑啉能同时有效抑制铜和钴的静态腐蚀。抑制剂的比重可以为0.01-10 %。其中优选比重为0.01-0.1%。
本发明提供的CMP抛光液PH值范围为3-5。抛光液PH值过低,在PH<2情况下事,抛光液容易造成铜布线的腐蚀,而且容易腐蚀设备。PH值属于中性区间时,即6<PH<8时,认为抛光液中硅溶胶不稳定。而PH值过高,PH>9时,容易造成low-k介质的损伤。所以PH值选为3-5比较合适。PH调节剂可选择稀释的硝酸和氢氧化钾。
附图说明
图1. (a)抛光前和(b)抛光后的互连结构截面示意图。
图2. 不同PH值条件下含有本发明所用抑制剂和不含抑制剂时钴的静态腐蚀速率。名称A1,A2,A3代表不含二巯基噻唑啉时的静态腐蚀速率。名称B1,B2,B3代表含15mM二巯基噻唑啉时的静态腐蚀速率。
具体实施方式
使用本抛光液的具体实施方式与传统的抛光液使用方式类似。在化学机械抛光工艺期间,晶片由抛光头支撑正面朝下,压在附有抛光垫的抛光台上,抛光液由泵的抽取和抛光台的旋转均匀的分散在晶片表面,由抛光头对晶片施加压力,抛光头和抛光台同时旋转达到去除晶片上多余铜以及介质表面的粘附层和阻挡层的目的。值得注意的是,以上所述使用方式是基于本领域传统抛光机而言,对特别的抛光机系统,可以根据实际情况合理调整执行方式同样能达到化学机械平坦化目的。附图1是抛光前互连结构截面示意图与抛光后形成的互连结构截面示意图。其中,介质可以是传统的二氧化硅,也可以是low-k介质;铜阻挡层材料可以是TaN,TiN,TaCN,TiCN等金属氮化物或者金属氮碳化合物,以及其他阻挡层材料。阻挡层的生长方式可以是PVD,ALD或者CVD;刻蚀阻挡层材料可以是SiN,SiC,SiCN以及其他难刻蚀的介质材料。通过使用本发明抛光液去除附图1(a)中上表面多余的铜以及介质上面的金属粘附层(Co)和阻挡层,从而形成附图1(b)所示结构。通过以下实施案例进一步阐述本发明的实施方式。
实施例1
抛光液配置:5wt%的硅溶胶;0.5wt%的双氧水;0.75wt%的甘氨酸(100毫摩尔浓度);0.06%-0.24wt%的二巯基噻唑啉(5mM-20mM浓度);以及余量的水。PH值调节至4.0;
抛光设备以及机械参数设置:本实施例所用抛光机为CETR公司生产的CP-4桌上型抛光机;机械参数设置为:压力为2psi,抛光液流速为100ml/min,抛光头转速为120rpm,抛光台转速为125rpm。
下面是用含不同二巯基噻唑啉浓度抛光液的钴抛光速率对比数据。
表一:钴在不同二巯基噻唑啉浓度抛光液中的抛光速率
二巯基噻唑啉浓度 | 0mM | 5mM | 10mM | 15mM | 20mM |
钴的抛光速率(nm/min) | 905 | 153 | 122 | 119 | 87 |
从表一数据可以看出,在抛光液中加入二巯基噻唑啉可以明显降低钴的抛光速率。由于实际互连结构中,粘附层的厚度不会超过5nm,所以粘附层抛光速率不应过快。本实施例通过在抛光液中加入二巯基噻唑啉后,可以极大降低钴的抛光速率,从不含二巯基噻唑啉时的905nm将至含5mM二巯基噻唑啉时的153nm。说明二巯基噻唑啉对钴的抑制作用是非常有效的。
实施例2
抛光液配置:5wt%的硅溶胶;0.5wt%的双氧水;0.75wt%的甘氨酸(100毫摩尔浓度);0.18wt%的二巯基噻唑啉(15mM浓度);以及余量的水。PH值分别调节至3.0,4.0,5.0;
抛光设备以及机械参数设置:本实施例所用抛光机为CETR公司生产的CP-4桌上型抛光机;机械参数设置为:压力为2psi,抛光液流速为100ml/min,抛光头转速为120rpm,抛光台转速为125rpm。
表二:不同PH值下,铜和钴在含与不含二巯基噻唑啉抛光液中的抛光速率以及选择比
从表二数据可以明显看到加入二巯基噻唑啉后,在各个PH值下,钴和铜的抛光速率都有所下降。表明在PH值为3-5的整个范围内,二巯基噻唑啉的对钴与铜都有抑制作用。在PH值=5,0mM二巯基噻唑啉抛光液中铜钽选择比最接近于1,但此条件下铜钴的抛光速率都过高不应采取。在PH值=3, 15mM二巯基噻唑啉抛光液中铜钴选择比为0.7,同时铜钴抛光速率较低,此抛光液配置为最佳。同时从附图2中可以看到,二巯基噻唑啉对钴的静态腐蚀抑制效率在PH值为3时也为最大。附图2还表明加入2巯基噻唑啉后,钴的静态腐蚀速率在各个PH值下都有很大降低。其中在PH值为3时降低最为明显。不同PH值下二巯基噻唑啉对钴的静态腐蚀抑制效率不同可能与二巯基噻唑啉在抛光液中的存在形式有关。对钴静态腐蚀的抑制有很大的意义,由于钴非常活泼,很容易在酸性溶液中溶解,而实际结构中钴的厚度不足5nm,所以抑制钴的静态腐蚀可防止沟槽侧墙处钴的溶解。
Claims (7)
1.一种基于金属Co的抛光工艺的抛光液,其特征在于该抛光液组分包括:氧化剂 0-5 % ,研磨颗粒 0.1-25 %,螯合剂 0.001-10 %,抑制剂 0.01-10 % ,水 余量;其中,百分比均为重量百分比,所述抑制剂为2巯基噻唑啉、2巯基苯骈噻唑或其它噻唑衍生物,或者为他们之中几种的混合物;抛光液PH值为3-5。
2.如权利要求1所述的抛光液,其特征在于,抛光液中氧化剂的含量为0.5%-5%。
3.如权利要求1或2所述的抛光液,其特征在于,所述氧化剂选自以下的至少一种:过氧化氢,过硫酸铵,高碘酸钾,高氯酸钾。
4.如权利要求1所述的抛光液,其特征在于,抛光液中研磨颗粒选自于以下的至少一种:二氧化硅,二氧化铈,三氧化二铝。
5.如权利要求4所述的抛光液,其特征在于,所述研磨颗粒粒径为10-100nm。
6.如权利要求1所述的抛光液,其特征在于,抛光液中螯合剂选择自:氨基酸,柠檬酸。
7.如权利要求6所述的抛光液,其特征在于,抛光液中螯合剂为甘氨酸。
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- 2011-12-05 JP JP2013523470A patent/JP2014509064A/ja active Pending
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WO2023284087A1 (zh) * | 2021-07-16 | 2023-01-19 | 张家港安储科技有限公司 | 一种用于在半导体晶圆清洗过程中的化学机械研磨后的清洗组合物 |
CN115160933A (zh) * | 2022-07-27 | 2022-10-11 | 河北工业大学 | 一种用于钴互连集成电路钴cmp的碱性抛光液及其制备方法 |
CN115160933B (zh) * | 2022-07-27 | 2023-11-28 | 河北工业大学 | 一种用于钴互连集成电路钴cmp的碱性抛光液及其制备方法 |
CN115820127A (zh) * | 2022-11-07 | 2023-03-21 | 上海交通大学 | 一种适用于铜钴互连结构的化学机械抛光液及其制备方法 |
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KR101439797B1 (ko) | 2014-09-11 |
CN102516875B (zh) | 2014-01-08 |
KR20130132389A (ko) | 2013-12-04 |
WO2013003991A8 (zh) | 2013-04-04 |
EP2592122A4 (en) | 2014-01-22 |
US20130140273A1 (en) | 2013-06-06 |
WO2013003991A1 (zh) | 2013-01-10 |
CN102516875A (zh) | 2012-06-27 |
EP2592122A1 (en) | 2013-05-15 |
JP2014509064A (ja) | 2014-04-10 |
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